Sorbitan esters and process for enzymatically preparing same

ABSTRACT

A process can be used for enzymatic preparation of sorbitan carboxylates. Sorbitan carboxylates are obtainable by this process.

FIELD OF THE INVENTION

The invention provides a process for enzymatic preparation of sorbitan carboxylates, and the sorbitan carboxylates obtainable by this process.

PRIOR ART

Sorbitol carboxylates are products of interest to the food and cosmetics industries not only on account of their surfactant properties, but also because of the possibility of obtaining them from natural and renewable raw materials.

DE102009001748A describes sorbitan esters obtained from the solvent-free reaction of 1 mol of sorbitol (also called glucitol) with 1.55 mol of caprylic acid, and the use of the sorbitan esters thus obtained as thickener for aqueous surfactant systems. It is a disadvantage of the process that, under the reaction conditions described, the sorbitol is dehydrated virtually completely, but at least partially, and forms what is called sorbitan (a product mixture).

Four degradation products of sorbitol that frequently occur under such conditions are the anhydrohexitols 1,4-anhydrosorbitol, 2,5-anhydrosorbitol, 1,5-anhydrosorbitol (Advances in Carbohydrate Chemistry and Biochemistry, 1983, 41, 27-66) and isosorbide (1,4:3,6-dianhydrosorbitol; ChemSusChem. 5 (1): 167-176).

A further disadvantage of these sorbitol esters is their dark colour, which requires aftertreatment, for example with activated carbon, in order to achieve product qualities usable in the cosmetics sector.

JP63133991 describes the reaction of 1.0 equivalent of oleic acid with 1.0 equivalent of sorbitol in the presence of >9% lipase (Candida Sp) at 40-50° C. and 100 mmHg (133 mbar). A disadvantage of this process described in the prior art is that only about 70% esterification is attained. A further disadvantage is that only pure oleic acid is used, which is too costly for industrial applications in the food and cosmetics sector and hence uneconomic.

DE3430944 describes the reaction of ≥4.0 equivalents of oleic acid or stearic acid with 1.0 equivalent of sorbitol in the presence of about 7% lipase at 40° C. for 72 h, wherein the reactants and the enzyme are reacted with one another in a concentration by mass of about 28 g per 1000 ml in an aqueous buffer system. A disadvantage of this process described in the prior art is the use of aqueous phosphate buffer, the salt burden of which in the product is undesirable for use in cosmetics. A further disadvantage is that the concentration by mass of the reactants and of the lipase in the buffer system is only about 3%, which means much too low a space-time yield for industrial conversions. A further disadvantage is that only pure oleic acid and pure stearic acid are used.

Lorie et al. describe, in Biotechnol. Bioeng. 1995, 48, 214-221, the reaction of sorbitol with 1.0 equivalent of oleic acid in the presence of 15% Novozym 435 (lipase from Candida antarctica; about 494 000 PLU per mole of fatty acid) at 90° C. and a pressure of <0.7 kPa (<7 mbar). One disadvantage of the process described in the prior art is that the sorbitol used remains as a highly viscous semisolid at the base of the reaction vessel, while oleic acid is the layer above it. This behaviour additionally complicates the mixing of the reactants, which is difficult in any case.

EP1755545B1 describes a mixture of sorbitan esters and sorbitol esters, wherein the chain length of the fatty acid of the sorbitan ester is greater than the chain length of the fatty acid of the sorbitol ester, and more than 80% saturated fatty acids is always used. The sorbitan esters are at least 50% of the mixture. The sorbitol esters consist solely of mono- and diesters, with at least 40% monoesters and less than 60% diesters, and are used to influence emulsion stability and viscosity. Proceeding from lauric acid, a mixture consisting of 7% sorbitan esters, 68% C12 sorbitol esters and 25% polyol is obtained. A disadvantage of the process for preparation described in the prior art is the fact that sorbitan esters are formed here too, as a result of which the hydrophilic portion of the surfactant is reduced, and a poor colour is also obtained.

The problem addressed by the present invention was that of providing a process for preparing sorbitan esters that is capable of overcoming at least one disadvantage of the prior art processes.

DESCRIPTION OF THE INVENTION

It has been found that, surprisingly, the object of the invention is achieved by the sorbitol carboxylates described hereinafter and the process described hereinafter.

It is an advantage of the present invention that the sorbitol carboxylates of the invention are excellent thickeners for aqueous surfactant systems compared to the prior art.

It is a further advantage that the sorbitol carboxylates of the invention also have excellent colour and very good odour compared to the prior art.

It is an advantage of the present invention that only very small amounts of sorbitol degradation products or esters of the degradation products are obtained as reaction products.

It is an advantage of the present invention that the process according to the invention can be performed in the absence of a solvent.

It is a further advantage of the present invention that the sorbitol carboxylates are obtained in a homogeneous reaction mixture, which means that no additional process steps such as extraction, crystallization, filtration or distillation are required.

An advantage of the present invention is that the process can be carried out at elevated temperatures. This leads to better miscibility of the co-reactants, while the recyclability of the enzyme used is surprisingly high.

It is a further advantage of the present invention that the sorbitol carboxylates obtained can be incorporated very readily into formulations, particularly into cosmetic formulations.

The present invention therefore provides a process for enzymatic preparation of a sorbitol carboxylate, comprising the process steps of

A) providing sorbitol and at least one acyl group donor, preferably fatty acid acyl group donor, selected in particular from fatty acid esters and fatty acids, more preferably fatty acids,

B) reacting sorbitol with the at least one acyl group donor in the presence of a lipase at a temperature of 75° C. to 110° C., preferably of 77° C. to 100° C., even more preferably 80° C. to 95° C., to give a sorbitol carboxylate, and optionally

C) purifying the sorbitol carboxylate,

characterized in that process step A) comprises blending the sorbitol and the at least one acyl group donor within a temperature range of 80° C. to 120° C., preferably of 90° C. to 120° C., even more preferably of 95° C. to 120° C., even more preferably of 100° C. to 120° C., for at least 10 minutes, preferably at least 30 minutes, even more preferably at least 60 minutes.

The term “sorbitol carboxylates” in the context of the present invention includes a composition that contains a majority of, especially at least 40% by weight, preferably at least 50% by weight, even more preferably at least 60% by weight, of carboxylic esters of sorbitol, based on the overall composition. However, as the case may be, by-products from the respective preparation processes may also be present, for example carboxylic esters of 1,4-anhydrosorbitol, carboxylic esters of 2,5-anhydrosorbitol, carboxylic esters of 1,5-anhydrosorbitol and carboxylic esters of isosorbide, and also unreacted reactants.

The terms “sorbitol carboxylates” and “sorbitan carboxylates” are used synonymously in the context of the present invention.

This use of the term is based on the common nomenclature for polyol esters, which are known to be prone to dehydration during their synthesis, and so the products are mixed compositions. Those skilled in the art will thus understand the term “sorbitan esters” to mean a mixture comprising not only esters of 1,4-anhydrosorbitol and esters of 1,5-anhydrosorbitol, but also esters of isosorbide and esters of sorbitol, and also free sorbitol; in this regard see also Food emulsifiers and their applications, 1997, page 26.

The term “carboxylic esters of sorbitol” in the context of the present invention refers to pure sorbitol compounds.

The term “carboxylic esters of 1,4-anhydrosorbitol” in the context of the present invention refers to pure 1,4-anhydrosorbitol compounds.

The term “carboxylic esters of 2,5-anhydrosorbitol” in the context of the present invention refers to pure 2,5-anhydrosorbitol compounds.

The term “carboxylic esters of 1,5-anhydrosorbitol” in the context of the present invention refers to pure 1,5-anhydrosorbitol compounds.

The term “carboxylic esters of isosorbide” in the context of the present invention refers to pure isosorbide compounds.

Unless stated otherwise, all stated percentages (%) are percentages by weight.

According to the invention, it is possible in accordance with the invention to use any acyl group donors. These include for example carboxylic esters or carboxylic acids themselves, and mixtures thereof.

It is preferable in accordance with the invention that the acyl group donor provided in process step A) provides acyl groups that derive from a carboxylic acid containing 2 to 34, preferably 4 to 24, more preferably 6 to 22, carbon atoms, especially a natural fatty acid or mixtures thereof.

Carboxylic esters used with preference in accordance with the invention as acyl group donor are selected from esters based on alkanols and polyols having up to 6 carbon atoms, particularly preferably having up to 3 carbon atoms, very particularly preferably glycerol esters.

Carboxylic esters used with particular preference in accordance with the invention as acyl group donor are selected from triglycerides, especially natural fats and oils, particularly preferably selected from the group comprising, preferably consisting of, coconut fat, palm kernel oil, olive oil, palm oil, argan oil, castor oil, linseed oil, babassu oil, rapeseed oil, algal oils, sesame oil, soya oil, avocado oil, jojoba oil, safflower oil, almond oil, cottonseed oil, shea butter, sunflower oil, cupuaçu butter and oils having a high proportion of polyunsaturated fatty acids (PUFAs). Sorbitan esters, monoglycerides and diglycerides, in particular containing the acyl groups described hereinbelow, may likewise preferably be used.

More preferably in accordance with the invention, the acyl group donor is selected from fatty acid acyl group donors that in particular provide an acyl group selected from the group of acyl groups of natural fatty acids, or mixtures thereof.

Preferred fatty acids in this connection are mixtures of natural fatty acids, especially mixtures in which no carboxylic acid chain length has a proportion in the overall chain length distribution of more than 95% by weight, especially more than 99% by weight.

Natural fatty acids can be produced on the basis of naturally occurring vegetable or animal oils and have preferably 6 to 30 carbon atoms, especially 8 to 22 carbon atoms. Natural fatty acids are generally unbranched and usually consist of an even number of carbon atoms. Any double bonds have cis configuration. Examples are: caproic acid, caprylic acid, capric acid, lauric acid, myristic acid, palmitic acid, palmifoleic acid, pelargonic acid (obtainable for example from the ozonolysis or oxidative cleavage of oleic acid), isostearic acid, stearic acid, 12-hydroxystearic acid, dihydroxystearic acid, undecylenic acid (obtainable for example from the pyrolysis of ricinoleic acid), oleic acid, linoleic acid, linolenic acid, petroselinic acid, elaidic acid, arachic acid, behenic acid, erucic acid, gadoleic acid, eicosapentaenoic acid, docosahexaenoic acid and arachidonic acid.

More preferably in accordance with the invention, the acyl group donor is selected from fatty acid acyl group donors that are characterized in that they provide an acyl group mixture containing at least two acyl groups of the carboxylic acids selected from the group of caproic acid, caprylic acid, capric acid, lauric acid, myristic acid, palmitic acid, palmitoleic acid, pelargonic acid (obtainable for example from the ozonolysis or oxidative cleavage of oleic acid), isostearic acid, stearic acid, 12-hydroxystearic acid, dihydroxystearic acid, undecylenic acid (obtainable for example from the pyrolysis of ricinoleic acid), oleic acid, linoleic acid, linolenic acid, petroselinic acid, elaidic acid, arachic acid, behenic acid, erucic acid, gadoleic acid, eicosapentaenoic acid, docosahexaenoic acid and arachidonic acid.

Acyl group donors used with preference in accordance with the invention are carboxylic acids, especially fatty acids. Preferred fatty acids in this connection are those mentioned above in connection with the fatty acids provided with preference.

Acyl group donors used alternatively with particular preference are mixtures of fatty acids with glycerol fatty acid esters, preference being given to using those mentioned above in connection with fatty acids provided with preference, both in the case of the fatty acids and in the case of the glycerol fatty acid components, with an identical degree of preference.

The mixture of fatty acid with glycerol fatty acid ester used preferably has a weight ratio of fatty acid to glycerol fatty acid ester of 80:20 to 99:1, preferably of 90:10 to 99:1, more preferably of 95:5 to 99:1.

A process preferred in accordance with the invention is characterized in that the sorbitol and the at least one acyl group donor make up at least 80% by weight, preferably at least 90% by weight, more preferably at least 95% by weight, based on the overall reaction mixture at the start of process step B).

Since the overall reaction mixture in this context consists largely of the reactants, i.e. sorbitol and acyl group donor, only very little solvent—if any—can he present in the overall reaction mixture. It is clear on the basis of the above that the acyl group donor is not covered by the term “solvent” in the process according to the invention.

Possible solvents would be for example ketones, for example methyl isohutyl ketone or cyclohexanone, sterically hindered secondary alcohols such as 2-butyl-1-octanol, methylcyclohexanols, 1-methoxy-2-propanol, butane-2,3-diol, 2-octanol, diacetone alcohol, 2-methyl-2-butanol, and ethers such as 1,4-dioxane, tetrahydrofuran and Varonic APM.

Based on the overall reaction mixture, solvents are present in a maximum total amount of less than 20% by weight, preferably less than 10% by weight, especially less than 5% by weight. The expression “is present in a maximum amount of less than X % by weight” can be equated with “has a content of less than X % by weight”.

Particular preference is given to carrying out the process according to the invention in the absence of solvent.

A process preferred in accordance with the invention is thus especially characterized in that, in process step B), the water content based on the overall reaction mixture is less than 15% by weight, preferably less than 5.0% by weight, more preferably less than 1.0% by weight.

Lipases used with preference in accordance with the invention in process step B) are present immobilized on a solid support.

Lipases used with preference in accordance with the invention in process step B) are lipases selected from the group comprising the lipase from Thermomyces lanuginosus (accession number O59952), lipases A and B (accession number P41365) from Candida antarctica and the lipase from Mucor miehei (accession number P19515), the lipase from Humicola sp. (accession number O59952), the lipase from Rhizomucor javanicus (accession number S32492), the lipase from Rhizopus oryzae (accession number P61872), the lipases from Candida rugosa (accession number P20261, P32946, P32947, P3294 and P32949), the lipase from Rhizopus niveus (accession number P61871), the lipase from Penicillium camemberti (accession number P25234), the lipases from Aspergillus niger (ABG73613, ABG73614 and ABG37906) and the lipase from Penicillium cyclopium (accession number P61869), particular preference being given to lipases A and B (accession number P41365) from Candida antarctica, and their respective at least 60%, with preference at least 80%, preferably at least 90% and especially preferably at least 95%, 98% or 99%, homologues at the amino acid level.

The accession numbers listed in the context of the present invention correspond to the ProteinBank database entries of the NCBI with a date of Jan. 1, 2017; generally, in the present context, the version number of the entry is identified by “.digit”, for example “.1”.

Enzymes that are homologous at the amino acid level preferably have, by comparison with the reference sequence, at least 50%, especially at least 90%, of the enzyme activity in propyl laurate units (PLU) as defined in the context of the present invention.

To determine the enzyme activity in PLU (propyl laurate units), 1-propanol and lauric acid are mixed homogeneously in an equimolar ratio at 60° C. The reaction is started with addition of enzyme and the reaction time is measured. Samples are taken from the reaction mixture at intervals and the content of converted lauric acid is determined by titration with potassium hydroxide solution. The enzyme activity in PLU results from the rate at which 1 g of the enzyme in question synthesizes 1 μmol of propyl laurate per minute at 60° C.; cf. in this respect also US20070087418, in particular [0185].

Commercial examples, and lipases that are likewise used with preference in processes according to the invention, are the commercial products Lipozyme TL IM, Novozym 435, Lipozyme IM 20, Lipase SP382, Lipase SP525, Lipase SP523, (all commercial products from Novozymes A/S, Bagsvaerd, Denmark), Chirazyme L2, Chirazyme L5, Chirazyme L8, Chirazyme L9 (all commercial products from Roche Molecular Biochemicals, Mannheim, Germany), CALB IMMO Plus TM from Purolite, and Lipase M “Amano”, Lipase F-AP 15 “Arnano”, Lipase AY “Amano”, Lipase N “Amano”, Lipase R “Amano”, Lipase A “Amano”, Lipase D “Amano”, Lipase G “Amano” (all commercial products from Amano, Japan).

“Homology at the amino acid level” is for the purposes of the present invention understood as meaning “amino acid identity”, which can be determined with the aid of known methods. In general, use is made of special computer programs with algorithms taking into account specific requirements. Preferred methods for determining the identity first generate the closest match between the sequences to be compared. Computer programs for determining the identity include, but are not limited to, the GCG program package including

-   -   GAP (Deveroy, J. et al., Nucleic Acid Research 12 (1984), page         387, Genetics Computer Group University of Wisconsin, Medicine         (WI), and     -   BLASTP, BLASTN and FASTA (Altschul, S. et al., Journal of         Molecular Biology 215 (1990), pages 403-410. The BLAST program         can be obtained from the National Center For Biotechnology         Information (NCBI) and from other sources (BLAST Handbook,         Altschul S. et al., NCBI NLM NIH Bethesda ND 22894; Altschul S.         et al., above).

Those skilled in the art are aware that various computer programs are available for the calculation of similarity or identity between two nucleotide or amino acid sequences. For instance, the percentage identity between two amino acid sequences can be determined for example by the algorithm developed by Needleman and Wunsch (J. Mol. Biol. (48): 444-453 (1970)), which has been integrated into the GAP program in the GCG software package (available at http://www.gcg.com), using either a Blossom 62 matrix or a PAM250 matrix, a gap weight of 16, 14, 12, 10, 8, 6 or 4 and a length weight of 1, 2, 3, 4, 5 or 6. Those skilled in the art will recognize that the use of different parameters will lead to slightly different results, but that the percentage identity between two amino acid sequences overall will not be significantly different. The Blossom 62 matrix is typically employed, using the default settings (gap weight: 12, length weight: 1).

In the context of the present invention, an identity of 60% according to the above algorithm means 60% homology. The same applies to higher identities.

In process step B), preference is given in accordance with the invention to using 500 PLU to 2000 PLU, preferably from 200 PLU to 1500 PLU, more preferably from 25 PLU to 1250 PLU, of lipase per gram of sorbitol to be converted.

Process step B) is in accordance with the invention preferably carried out at a pressure of less than 1 bar, preferably less than 0.5 bar and particularly preferably less than 0.1 bar.

Process step B) is in accordance with the invention alternatively preferably carried out in a bubble column reactor, with at least one inert gas being passed through the reaction mixture; this gas is preferably selected from the group comprising, preferably consisting of, nitrogen and argon. In this connection, it is preferable in accordance with the invention for the gas stream to be 1 to 60 kg/h, preferably 5 to 25 kg/h, yet more preferably 10 to 14 kg/h.

Process step B) is in accordance with the invention preferably characterized in that process step B) is ended no later than 180 hours, preferably 120 hours, particularly preferably 100 hours, after the lipase has been added.

A process that is preferred in accordance with the invention is characterized in that the molar ratio of sorbitol provided to acyl groups present in all acyl group donors provided is within a range from 1.00:0.50 to 1.00:5.00, preferably from 1.00:0.70 to 1.00:3.00, particularly preferably from 1.00:1.00 to 1.00:2.25, alternatively particularly preferably from 1.00:2.3 to 1.00:4.50.

A process that is preferred in accordance with the invention is characterized in that by-products formed in process step B), for example water when the acyl group donor used is an acid and the corresponding alcohol when the acyl group donor used is an ester, are removed.

This is possible by distillation for example.

Process step C) of the process of the invention comprises the purification of the sorbitol carboxylate.

All methodologies that allow the sorbitol carboxylate to be obtained in higher concentration can be employed for this purpose.

It is in accordance with the invention preferable that the process according to the invention includes the removal, in process step C), of the lipase used in the process according to the invention.

When the lipase is mmobilized on a support, it is preferable in accordance with the invention that the lipase is removed by filtration through a filter, especially a bag filter, having a fineness of 0.1 μ to 1250 μ, preferably of 0.5 μ to 100 μ.

The process of the present invention is preferably in accordance with the invention characterized in that it does not involve any use of a molecular sieve.

The process of the present invention is preferably in accordance with the invention characterized in that the substrates are not immobilized on solid supports such as silica.

The present invention further provides the sorbitol carboxylate obtainable by the process of the invention.

Preference is given in accordance with the invention to sorbitol carboxylates comprising carboxylic esters of sorbitol, carboxylic esters of 1,4-anhydrosorbitol, carboxylic esters of 2,5-anhydrosorbitol, carboxylic esters of 1,5-anhydrosorbitol, and carboxylic esters of isosorbide, where the ratio by weight of the sorbitol residues present in the sorbitol carboxylate to the sum total of all the 1,4-anhydrosorbitol residues, 2,5-anhydrosorbitol residues and 1,5-anhydrosorbitol residues and isosorbide residues present in the sorbitol carboxylate is greater than 90:10, preferably greater than 93:7, more preferably greater than 95:5, most preferably greater than 96:4, characterized in that the molar ratio of esterified primary hydroxyl groups to esterified secondary hydroxyl groups in the carboxylic esters of sorbitol is 80:20 to 20:80, preferably 70:30 to 30:70, even more preferably 60:40 to 40:60, even more preferably from 55:45 to 45:55.

It is clearly apparent from the expression “sorbitol carboxylates containing carboxylic esters of sorbitol, carboxylic esters of 1,4-anhydrosorbitol, carboxylic esters of 2,5-anhydrosorbitol, carboxylic esters of 1,5-anhydrosorbitol and carboxylic esters of isosorbide, where the weight ratio of the sorbitol residues present in the carboxylic esters to the sum total of all 1,4-anhydrosorbitol residues, 2,5-anhydrosorbitol residues, 1,5-anhydrosorbitol residues and isosorbide residues present in the carboxylic esters is greater than 90:10” that the content of at least one selected from carboxylic esters of 1,4-anhydrosorbitol, carboxylic esters of 2,5-anhydrosorbitol, carboxylic esters of 1,5-anhydrosorbitol and carboxylic esters of isosorbide must be non-0 (zero), since divisions by 0 are undefined.

The weight ratio of the sorbitol residues present in the sorbitol carboxylates according to the invention to the sum total of all 1,4-anhydrosorbitol residues, 2,5-anhydrosorbitol residues, 1,5-anhydrosorbitol residues and isosorbide residues present in the sorbitol carboxylate according to the invention is determined by means of high-performance liquid chromatography (HPLC). This method includes the alkaline hydrolysis of the sorbitol carboxylate to be analysed, removal of the carboxylic acids and analysis of the sorbitol and the 1,4-anhydrosorbitol, 2,5-anhydrosorbitol, 1,5-anhydrosorbitol and isosorbide degradation products thereof.

For this purpose, an initial charge of 150 mg of the sorbitol carboxylate to be analysed in 2.00 ml of 1 M aqueous KOH solution is hydrolysed at 95° C. with stirring for 30 min. The reaction solution is then cooled to room temperature and adjusted to pH 2-3 with 2 M aqueous HCl solution. The carboxylic acids that precipitate out as a result are then extracted with diethyl ether (3×3.00 ml), with removal of the organic supernatant by pipette after each extraction. After the extraction, the aqueous solution is heated to 50° C. with stirring for 20 min, which removes the rest of the ether (boiling point of diethyl ether: 34.6° C.).

The solution obtained above is made up to 10.0 ml with bidistilled H₂O and then diluted 1:10, and an aliquot of the solution is analysed by HPLC. The analysis is carried out under the following conditions:

Column: Aminex HPX-87C column 300×7.8 mm

Eluent: H₂O

Injected volume: 10.0 μl

Flow rate: 0.60 ml/min

Column temperature: 50° C.

Detector: G1362A/1260 RID (from Agilent), 35° C.

Run time: 30.0 min

Sorbitol and its degradation products are separated by an ion-exchange process.

For the evaluation, the peak area of sorbitol is expressed relative to the sum total of the peak areas of 1,4-anhydrosorbitol, 2,5-anhydrosorbitol, 1,5-anhydrosorbitol and isosorbide.

Reference substances for the sorbitol degradation products are commercially available or can alternatively be obtained by heating sorbitol in neat form in the presence of acidic (>140° C.) or basic (>180° C.) catalysts.

The molar ratio of esterified primary hydroxyl groups to esterified secondary hydroxyl groups in the carboxylic esters of sorbitol is determined by ¹³C NMR spectroscopy. For sample preparation, 50-70 mg of substance is dissolved in 1 ml of a deuterated solvent to which has been added a relaxation agent (chromium(III) acetylacetonate, 1%). DMSO-d6, CDCl₃ and methanol-d4 have been found to be suitable solvents, according to product properties. If the sample does not dissolve completely in one of the solvents, a solvent mixture must be found. The prepared sample solution is transferred to a 5 mm NMR tube and introduced into the NMR spectrometer.

The NMR spectroscopy investigations can in principle be carried out with any commercial NMR instrument. For the present NMR spectroscopy investigations, a Bruker Avance 400 instrument was used. The spectra were recorded with the following parameters:

Temperature: T=295 K, Time delay: D1=2 s. Number of scans: NS=2048, Transmitter frequency offset: O1P=110 ppm, Sweep width: SW=300 ppm, Probe: PA BBI 400 S1 H-BB-D-05-Z.

The resonance signals were recorded against the chemical shift of tetramethylsilane (TMS=0 ppm) as internal standard. Other commercial NMR instruments give comparable results with the same operating parameters. The signals are quantified by determining the area under the respective resonance signals, i.e. the area enclosed by the signal from the baseline. In the present NMR spectroscopy investigations, the spectra were integrated using the “TOPSPIN” software, version 3.0.

For more accurate identification of the esterified primary and esterified secondary hydroxyl groups, a DEPT spectrum is first recorded. The molar ratio of esterified primary to esterified secondary hydroxyl groups is determined by subtracting the integral value P (group of signals for the esterified primary hydroxyl groups) from integral value C (group of signals for the ester carbonyl groups).

This gives an internal value S for the group of signals for the esterified secondary hydroxyl groups, which cannot be determined directly because of superimposition with other signals.

P=Integral value of the esterified primary hydroxyl groups [R—CH₂—OC(O)R groups]

C=Integral value of the ester carbonyl groups

S=C−P=Integral value of the esterified secondary hydroxyl groups [R₂—CH—OC(O)R groups]

The ratio of P to S ascertained corresponds to the molar ratio of esterified primary hydroxyl groups to esterified secondary hydroxyl groups in the carboxylic esters of sorbitol.

Preference is given in accordance with the invention to sorbitol carboxylates that are characterized in that the average degree of esterification of the carboxylic esters of sorbitol present is from 0.3 to 4.0, preferably from 1.0 to 3.0, more preferably from 1.1 to 2.7, especially preferably from 1.3 to 2.6. Preference is alternatively given in accordance with the invention to sorbitol carboxylates that are characterized in that the average degree of esterification of the carboxylic esters of sorbitol present is from 2.7 to 4.0.

The average degree of esterification of the carboxylic esters of sorbitol present in the sorbitol carboxylate according to the invention is determined, for example, by first determining the content of free sorbitol and of its 1,4-anhydrosorbitol, 2,5-anhydrosorbitol, 1,5-anhydrosorbitol and isosorbide degradation products in a sample of the sorbitol carboxylate in question. It is additionally necessary to determine the saponification value, acid value and content of free and neutralized fatty acids (for example via GC as described hereinbelow under “Determination of the content of free carboxylic acid”). The determination of the carboxylic acid composition after alkaline saponification gives an average molar mass of the carboxylic acid mixture that has been esterified.

This value can then be used to calculate the average degree of esterification.

Preference is given in accordance with the invention to a sorbitol carboxylate that is characterized in that the carboxylic esters of sorbitoi present comprise monoesters of sorbitol, diesters of sorbitol and triesters of sorbitol, where the triesters of sorbitol are present preferably in an amount, based on all carboxylic esters of sorbitol present, of 10% to 50% by weight, preferably of 15% by weight to 45% by weight, more preferably of 20% by weight to 40% by weight. In this connection, it is further preferable in accordance with the invention that the carboxylic esters of sorbitol present comprise monoesters of sorbitol, diesters of sorbitol, triesters of sorbitol and tetraesters of sorbitol.

Preference is given in accordance with the invention to a sorbitol carboxylate that is characterized in that it contains 0.05% to 40% by weight, preferably 0.2% to 25% by weight, more preferably 0.5% to 10% by weight, of free sorbitol,

where the percentages by weight are based on the overall sorbitol carboxylate.

For determination of the sorbitol present in the sorbitol carboxylate of the invention by GC, a portion of the sample is dissolved in pyridine:chloroform (4:1). 0.25 ml of this solution is mixed with 0.5 ml of MSTFA [N-methyl-N-(trimethylsilyl)trifluoroacetamide] and 0.5 ml of a mixture of N-trimethylsilylimidazole and pyridine (11:39).

The alcohols are quantitatively converted into their trimethylsilyl ethers by reaction at 80° C. (30 minutes) and then analysed by GC/FID.

This is performed in a gas chromatograph equipped with a split/splitless injector, a capillary column and a flame ionization detector, under the following conditions:

Injector: 290° C., split 30 ml

Injected volume: 1 μl

Column: 50 m*0.32 mm HP5 1.05 μm

Carrier gas: Hydrogen, constant flow, 2 ml/min

Temperature program: 100° C. to 140° C. at 10° C./min, then 140° C. to 300° C. at 5° C./min, then conditioning at 300° C. for 5 minutes.

Detector: FID at 310° C. Hydrogen 30 min Air 400 ml/min Make-up gas 12 ml/min

The sorbitol is separated off and its proportion by mass determined by an internal standard method. For this purpose, the GC system is calibrated by analysing mixtures of sorbitol and of the internal standard of known composition.

Preference is given in accordance with the invention to a sorbitol carboxylate that is characterized in that it contains less than 25% by weight, preferably from 0.01% by weight to 20% by weight, more preferably from 0.05% by weight to 10% by weight, of at least one free carboxylic acid, the percentages by weight being based on the overall sorbitol carboxylate.

The at least one free carboxylic acid may be in protonated or neutralized form.

To determine the content of free carboxylic acid in the sorbitol carboxylate of the invention, the acid value is first determined. Through the acid value and molecular weight of the fatty acid concerned, it is possible to determine the proportion by weight.

Suitable methods for determining the acid number are particularly those according to DGF C-V 2, DIN EN ISO 2114, Ph. Eur. 2.5.1, ISO 3682 and ASTM D 974.

It is known to those skilled in the art that, where there is a mixture of carboxylic acids, a GC analysis can also additionally be carried out after saponification of the sorbitol carboxylate, in order to determine an average molecular weight of the carboxylic acid mixture present.

For this purpose, 0.6 g of the sorbitol carboxylate of the invention is boiled under reflux in 25 ml of 0.5 M ethanolic KOH solution for 4 hours. The pH is then adjusted to 2-3 with sulfuric acid and the liberated carboxylic acids are separated by extracting three times with a volume of petroleum ether.

The combined extracts are concentrated to about 10 ml by evaporation.

Suitable methods for determining the fatty acid distribution are in particular those according to DGF C VI 11a, DGF C-VI 10 a and GAT ring test 7/99.

A 0.5 ml aliquot of the petroleum ether extract obtained as described above is mixed in an autosampler vial with 0.5 ml of MTBE and 1 ml of trimethylanilinium hydroxide (0.2 M in methanol) and analysed by GC. This is performed in a gas chromatograph equipped with a split/splitless injector, a capillary column and a flame ionization detector, under the following conditions:

Injector: 290° C., split 30 ml

Injected volume: 1 μl

Column: 30 m*0.32 mm HP1 0.25 μm

Carrier gas: Helium, head pressure 70 kPa

Temperature program: 80° C.-300° C. at 8° C./min, then conditioning for 20 minutes at 300° C.

Detector: FID at 320° C. Hydrogen 35 ml/min Air 240 ml/min Make-up gas 12 ml/min

The carboxylic acids are separated according to length of their carbon chain in the form of their methyl esters. By evaluating the peak areas it is possible to determine the mass ratio of these carboxylic acid methyl esters to one another and from this—via their respective molecular weights—their molar ratio, which corresponds to the molar ratio of the associated carboxylic acids. it is in addition possible to determine an average molecular weight of this fatty acid mixture:

$a_{i} = {\frac{A_{i}}{\sum\limits_{i}A_{i}} \cdot 100}$

where a_(i)=Normalized proportion by mass of carboxylic acid methyl ester i in the mixture of all carboxylic acid methyl esters [%]. A_(i)=Peak area of carboxylic acid methyl ester i in the GC chromatogram [%].

$n_{i} = \frac{a_{i}}{\left( {M_{i} + 14} \right)}$

where n_(i)=Molar amount [mol] of carboxylic acid methyl ester i in 100 g of carboxylic acid methyl ester mixture; from this, the ratios of the individual n_(i) values to one another are obtained, which correspond to the ratios of the molar amounts of the associated carboxylic acids in the sorbitol carboxylate; thus it is possible for the total molar amount n_(s) [mol] of carboxylic acids in 1 g of sorbitol carboxylate, as obtained from the saponification value (see below), to be split into its components according to said ratios. M_(i)=Molecular weight of the carboxylic acid corresponding to methyl ester i [g/mol].

$\begin{matrix} {\overset{\_}{M_{s}} = {\sum\limits_{i}\left( {\frac{n_{i}}{\sum\limits_{i}n_{i}} \cdot M_{i}} \right)}} & {where} & {\overset{\_}{M_{s}} = {{{Average}{molecular}{weight}{of}{the}{mixture}{of}{carboxylic}{{acids}.n_{i}}} = {{{Molar}{{amount}\lbrack{mol}\rbrack}{of}{carboxylic}{}{acid}{methyl}{ester}i{in}100g{of}{carboxylic}{acid}{methyl}{ester}{{mixture}.M_{i}}} = {{Molecular}{weight}{of}{the}{carboxylic}{acid}{{i\left\lbrack {g/{mol}} \right\rbrack}.}}}}} \end{matrix}$

Preference is given in accordance with the invention to a sorbitol carboxylate that is characterized in that the total monoester component of the carboxylic ester of sorbitol contains from 5% by weight to 25% by weight, preferably from 7% by weight to 15% by weight, more preferably from 9% by weight to 13% by weight, of secondary ester regiolsomers.

Preference is given in accordance with the invention to a sorbitol carboxylate that is characterized in that the total monoester component of the carboxylic ester of sorbitol and the total diester component of the carboxylic ester of sorbitol each comprise at least two regioisomers.

Preference is given in accordance with the invention to a sorbitol carboxylate that is characterized in that the total diester component of the carboxylic ester of sorbitol contains from 25% by weight to 45% by weight, preferably from 28% by weight to 39% by weight, more preferably from 30% by weight to 37% by weight, of regioisomers in which at least one secondary hydroxyl group has been esterified.

The determination of the content of secondary ester regiolsomer in the total monoester component of the carboxylic ester of sorbitol of the invention, the determination of the content of triester species based on the sum total of all carboxylic esters of sorbitol that are present, and the determination of the content of regioisorners in the total diester component in which at least one secondary hydroxyl group has been esterified can be performed by gas chromatography, optionally coupled with mass spectrometry (GC-FID and GC-MS):

10 mg of a sample of the corresponding sorbitol carboxylates is first dissolved in 1.5 ml of trichloromethane, and then 0.15 ml of N-methyl-N-(trimethylsilyl)trifluoroacetamide (MSTFA) is added. The derivatization is carried out at 80° C. for 30 minutes. A sample of the clear solution thus obtained is analysed by GC-FID and GC-MS. The parameters of the analysis method are:

Gas chromatograph: Agilent MSD 7890

Column: Agilent HP-5 (50 m, 0.32 mm, 0.5 μm),

Flow rate: constant 2 ml/min with hydrogen (GC-MS: helium)

Thermal equilibration at 80° C., 8° C./min; 300° C., 30 min, injector 1 μl, split 1:20, detector at 310° C.

Detector: FID, 310° C./GC-MS scan 35-650 d

In the GC-FID analysis, the esters present in the sample are separated according to their total chain length. The ratios of the individual ester species to one another are determined via the respective area percentage of the GC-FID peak. The peaks are identified/assigned to the individual ester species via GC-MS, if appropriate also via a comparison of retention time of separately prepared and isolated standards, for example for the mono- and diesters esterified exclusively at primary hydroxyl groups.

This method can likewise be used to detect the content of free protonated and also free neutralized carboxylic acids, since these are likewise derivatized.

The present invention further provides for the use of the sorbitol carboxylates according to the invention as viscosity regulator, care active ingredient, foam booster or solubilizer, antimicrobial, antistat, binder, corrosion inhibitor, dispersant, emulsifier, film former, humectant, opacifier, oral care agent, preservative, skincare agent, hydrophilic emollient, foam stabilizer and nonionic surfactant, preferably as viscosity regulator, emulsifier, antimicrobial and hydrophilic emollient, particularly preferably as viscosity regulator, especially as thickener, especially in cleansing or care formulations.

The examples that follow describe the present invention by way of example, without any intention to limit the invention, the scope of application of which is apparent from the entirety of the description and the claims, to the embodiments specified in the examples.

EXAMPLES

Various sorbitol carboxylates were synthesized as described hereinafter.

Method for Determining Colour Numbers

A 25% solution of the sample to be analysed was prepared in a mixture of concentrated acetic acid and toluene (3:1), and filtered if necessary to give a clear solution. An aliquot (approx. 10 g; so that the cuvette is sufficiently filled) was measured in a Lica 690 spectral colorimeter at room temperature in an 11 mm round cuvette, and the colour numbers reported in each case were recorded.

Example 1: Enzymatic Esterification of Sorbitol with 1.55 eq. of Caprylic Acid (According to the Invention)

A mixture of sorbitol (96.5 g, 0.529 mol, 1.00 eq.) and caprylic acid (acid number=389 mg KOH/g, >98%, 118.34 g, 0.821 mol, 1.55 eq.) was heated to 100° C. while stirring and passing N₂ through. After 1 h, the mixture was cooled down to 85° C., immobilized Candida antarctica lipase B enzyme (6.44 g; Purolite D5619, corresponding to 55747 PLU) was added, and stirring of the mixture was continued at 85° C. and 15 mbar for 24 h, during which time the water formed was distilled off continuously. The mixture was then filtered at 80° C. through a Büchner funnel with black band filter to remove the enzyme. The product obtained had an acid number of 3.0 mg KOH/g.

Example 1B: Sorbitan Ester According to “Example 0” in DE102009001748A (Not According to the Invention)

A mixture of sorbitol (70% aqueous solution, 390.45 g, 1.50 mol, 1.00 eq.), phosphoric acid (2.9 g) and sodium hydroxide (5.0 g) was dehydrated at 140° C. for 30 min. Subsequently, caprylic acid (acid number=389 mg KOH/g, >93%, 334.8 g, 2.32 mol, 1.55 eq.) was added, and the mixture was stirred at 200° C. until an acid number of 8.1 mg KOH/g had been attained.

Example 1C: Enzymatic Esterification of Sorbitol with 1.55 eq. of Caprylic Acid According to Biotechnol Bioeng 1995 48 214-221 (Not According to the Invention)

A mixture of sorbitol (96.5 g, 0.529 mol, 1.00 eq.), caprylic acid (acid number=389 mg KOH/g, >98%, 118.34 g, 0.821 mol, 1.55 eq.) and Novozym 435 (57.9 g, 405475 PLU) was stirred at 90° C. and <7 mbar for 24 h, and the water formed was distilled off continuously. The mixture was then filtered at 85° C. through a Büchner funnel with black band filter to remove the enzyme. The product obtained had an acid number of 2.0 mg KOH/g.

Example 2: Enzymatic Esterification of Sorbitol with 2.00 eq. of Technical Grade Oleic Acid (According to the Invention)

A mixture of sorbitol (51.3 g, 0.282 mol, 1.00 eq.) and oleic acid (acid number=200 mg KOH/g, iodine number=92.3 g I₂/100 g, 157.9 g, 0.563 mol, 2.00 eq.) was heated to 100° C. while stirring and passing N₂ through. After 1 h, the mixture was cooled down to 85° C., immobilized Candida antarctica lipase B enzyme (6.28 g; Purolite D5619, corresponding to 54361 PLU) was added, and stirring of the mixture was continued at 85° C. and 20 mbar for 24 h, during which time the water formed was distilled off continuously. The mixture was then filtered at 80° C. through a Büchner funnel with black band filter to remove the enzyme. The product obtained had an acid number of 4.2 mg KOH/g.

Example 2B: Enzymatic Esterification of Sorbitol with 1.00 eq. of Oleic Acid According to Biotechnol Bioeng 1995 48 214-221 (Not According to the Invention)

A mixture of sorbitol (100.1 g, 0.549 mol, 1.00 eq.), oleic acid (>99%, 155.1 g, 0.549 mol, 1.00 eq.) and Novozym 435 (38.7 g, 271126 PLU) was stirred at 90° C. and <7 mbar for 24 h, and the water formed was distilled off continuously. The mixture was then filtered at 85° C. through a Büchner funnel with black band filter to remove the enzyme. The product obtained had an acid number of 12.8 mg KOH/g.

Example 3: Enzymatic Esterification of Sorbitol with 1.50 eq. of Stearic Acid (According to the Invention)

A mixture of sorbitol (62.6 g, 0.344 mol, 1.00 eq.) and stearic acid (acid number=198 mg KOH/g, ≥92%, 146.7 g, 0.516 mol, 1.50 eq.) was heated to 115° C. while stirring and passing N₂ through.

After 1 h, the mixture was cooled down to 90° C., immobilized Candida antarctica lipase B enzyme (6.28 g; Purolite D5619, corresponding to 54350 PLU) was added, and stirring of the mixture was continued at 90° C. and <7 mbar for 24 h, during which time the water formed was distilled off continuously. The mixture was then filtered at 85° C. through a Büchner funnel with black band filter to remove the enzyme. The product obtained had an acid number of 6.5 mg KOH/g.

Example 3B: Enzymatic Esterification of Sorbitol with 1.50 eq. of Stearic Acid According to Biotechnol Bioeng 1995 48 214-221 (Not According to the Invention)

A mixture of sorbitol (62.6 g, 0.344 mol, 1.00 eq.), stearic acid (acid number=198 mg KOH/g, ≥92%, 146.7 g, 0.516 mol, 1.50 eq.) and Novozym 435 (7.77 g, 54393 PLU) was stirred at 90° C. and <7 mbar for 24 h, and the water formed was distilled off continuously. The mixture was then filtered at 85° C. through a Büchner funnel with black band filter to remove the enzyme. The product obtained had an acid number of 10.4 mg KOH/g.

Example 4: Enzymatic Esterification of Sorbitol with 1.80 eq. of Lauric Acid (According to the Invention)

A mixture of sorbitol (71.4 g, 0.392 mol, 1.00 eq.) and lauric acid (acid number=280 mg KOH/g, ≥99%, 141.3 g, 0.705 mol, 1.80 eq.) was heated to 100° C. while stirring and passing N₂ through. After 1 h, the mixture was cooled down to 95° C., immobilized Candida antarctica lipase B enzyme (6.38 g; Purolite D5619, corresponding to 55227 PLU) was added, and stirring of the mixture was continued at 95° C. and 20 mbar for 24 h, during which time the water formed was distilled off continuously. The mixture was then filtered at 80° C. through a Büchner funnel with black band filter to remove the enzyme. The product obtained had an acid number of 3.5 mg KOH/g.

Example 4B: Sorbitol Ester According to “Preparation (ii), (a)” from EP1755545B1 (Not According to the Invention)

A mixture of sorbitol (70% aqueous solution, 390.0 g, 1.50 mol, 1.00 eq.), lauric acid (acid number=280 mg KOH/g, ≥99%, 330.0 g, 1.65 mol, 1.10 eq.) and K₂CO₃ (16 g) were heated to 180° C. while stirring and passing N₂ through, and the water formed was distilled off continuously until an acid number of 3.5 mg KOH/g had been attained.

Example 4C: Sorbitol Ester According to “Preparation (ii),(b)” from EP1755545B1 (Not According to the Invention)

A mixture of sorbitol (99.0 g, 0.54 mol, 1.00 eq.), methyl laurate (140.0 g, 0.65 mol, 1.20 eq.) and K₂CO₃ (6 g) was heated to 160° C. at 50 mbar while stirring for 5 h, during which time the methanol formed was distilled off continuously.

Example 4D: Enzymatic Esterification of Sorbitol with 1.80 eq. of Lauric Acid According to Biotechnol Bioeng 1995 48 214-221 (Not According to the Invention)

A mixture of sorbitol (71.4 g, 0.392 mol, 1.00 eq.), lauric acid (acid number=280 mg KOH/g, ≥99%, 141.3 g, 0.705 mol, 1.80 eq.) and Novozym 435 (49.8 g, 348253 PLU) was stirred at 90° C. and <7 mbar for 24 h, and the water formed was distilled off continuously. The mixture was then filtered at 85° C. through a Büchner funnel with black band filter to remove the enzyme. The product obtained had an acid number of 2.8 mg KOH/g.

Example 5: Characterization of the Sorbitol Carboxylates

Table 1 compares the parameters determined for the examples according to the invention and the noninventive examples.

More particularly, it is apparent from Examples 4, 4B and 4C that the sorbitol carboxylates prepared by the process according to the invention have a better colour than those from the conventional chemical synthesis.

TABLE 1 Inventive examples are marked by * NMR Sorbitol: Iodine colour prim. vs. degradation number in sec. ester products solution Example 1 * 49:51 98:2 0.1 Example 1B n.a.  14:86 2.1 Example 1C 43:57 98:2 0.1 Example 2* 48:52 98:2 0.1 Example 2B 48:52 97:3 0.8 Example 3* 46:54 99:1 0.1 Example 3B 45:55 98:2 0.1 Example 4* 47:53 98:2 0.1 Example 4B 47:53  89:11 2.2 Example 4C 34:66  78:22 1.0 Example 4D 47:53 98:2 0.1

Example 6: Thickening Performance in Cosmetic Formulations

The thickening action of the inventive examples was evaluated by comparison with the corresponding noninventive examples in two different formulations:

Formulation 1 consisted of 9% SLES, 3% Cocamidopropyl Betaine and 0.7% NaCl in water. The pH of formulation 1 was adjusted to 5.2 with citric acid. Subsequently incorporated into this formulation in each case was 1.1% of the example substances mentioned above by stirring at 60° C. for 30 min, and the viscosities were measured using a Brookfield viscometer (spindle 62, 30 rpm, in Examples 1, 1B, 1C, 2, 2B; spindle 2, 60 rpm, in Examples 3, 3B, 4, 4B, 4C, 4D) at 22° C.

Formulation 2 consisted of 5.6% AM C, 4.4% Lauryl Glucoside, 1.2% Coco-Glucoside and 3.6% Glutamate in water. The pH of formulation 2 was adjusted to 5.2 with citric acid. Subsequently incorporated into this formulation in each case was 1.0% of the example substances mentioned above by stirring at 60° C. for 30 min, and the viscosities were measured using a Brookfield viscometer (spindle 62, 30 rpm, in Examples 1, 1B, 1C, 2, 2B; spindle 2, 60 rpm, in Examples 3, 3B, 4, 4B, 4C, 4D) at 22° C.

The results of the viscosity measurements are shown in Table 2.

TABLE 2 Viscosity of the example formulation containing 1.1% thickener Viscosity of Viscosity of formulation formulation Example 1 [mPa*s] 2 [mPa*s] 1 inventive 6517 4341 1B noninventive 6221 3723 1C noninventive 4627 1877 2 inventive 93  350 2B noninventive 42  170 3 inventive 50  144 3B noninventive 26    98^(§) 4 inventive 74 2027 4B noninventive 50 1000 4C noninventive 21  981 4D noninventive 35  200 ^(§)Example 3B was not fully soluble in formulation 2, which is a further disadvantage of this noninventive example.

The results from Table 2 show that higher viscosities are achieved with the inventive Example 1 in both formulations than with the noninventive Examples 1B and 1C, The same is found for the inventive Example 2 compared to the noninventive Example 2B, and for 3 versus 3B and 4 versus 4B, 4C and 4D.

Example 7: Accelerated Enzymatic Reaction

The literature Biotechnol Bioeng 1995 48 214-221 describes the use of extremely high amounts of enzyme, namely about 494 000 PLU per mole of fatty acid used. Such a high enzyme load is uneconomic. Loads of interest are around 100 000 PLU per mole of fatty acid used or lower. In the case of Examples 3 (inventive) and 3B (noninventive), after the reaction had ended and after the enzyme had been removed, the acid number was determined and an aliquot (about 30 g) in a 100 ml glass measuring cylinder was left in a heated cabinet at 90° C. for 24 h and then, after the phases had separated, the ratio (v/v) of the upper ester phase to the lower sorbitol phase was determined.

Table 2 presents the results.

TABLE 2 Acid number and ratio (v/v) of ester to sorbitol phase Acid number Ratio (v/v) [mg KOH/g] of ester to Enzyme load per after reaction sorbitol mole of fatty acid time 24 h phase Example inventive about 105 000 6.5 89:11 3 Example Non- about 105 000 10.4 83:17 3B inventive

It becomes clear from the data shown in Table 2 that the process according to the invention has the advantage compared to the process described in the prior art that, after a reaction time of 24 h, a low acid number has already been attained, which is desirable, and the sorbitol phase that separates in the melt likewise represents a smaller proportion.

A further advantage of the process according to the invention is found in a comparison of Example 1 with 1C. In spite of seven times the amount of lipase, after a reaction time of 24 h, in the prior art process, the conversion rate measured by the acid number is within the same range as in the process according to the invention.

TABLE 3 Acid value Enzyme load Acid number [mg per mole of KOH/g] after reaction fatty acid time 24 h Example 1 inventive about 68 000 3.0 Example 1C Non-inventive about 500 000 2.0

A similar picture is found in a comparison of Example 2 with 2B. With the same amount of lipase, after a reaction time of 24 h, in the prior art process, the conversion rate measured by the acid number is actually clearly lower than in the process according to the invention.

TABLE 4 Acid value Enzyme load Acid number [mg per mole of KOH/g] after reaction fatty acid time 24 h Example 2 inventive about 97 000 4.2 Example 2B noninventive about 500 000 12.8

A similar picture is found in a comparison of Example 4 with 4D. With the same amount of lipase, after a reaction time of 24 h, in the prior art process, the conversion rate is within the same range as in the process according to the invention.

TABLE 5 Acid value Enzyme load Acid number [mg per mole of KOH/g] after reaction fatty acid time 24 h Example 4 inventive about 78,000 3.5 Example 4D noninventive about 500 000 2.8

Example Formulations Recipes 1a, 1b and 1c: Antiperspirant/Deodorant Formulations Containing Aluminium Salts

Recipe 1a 1b 1c Composition from example 3 3.2% 3.2% 3.2% C18-C22 Hydroxyalkyl Hydroxypropyl Guar 0.2% (ESAFLOR HM 22, Lamberti S.p.A.) Hydroxypropyl Guar (ESAFLOR HDR, Lamberti 0.2% 0.2% S.p.A.) Isoamyl Cocoate (TEGOSOFT ® AC, Evonik 5.4% 5.4% 5.4% Operations GmbH) Water ad 100% ad 100% ad 100% Aluminium Chlorohydrate (50% aq.; Locron LIC, 20.0%  20.0%  20.0%  Clariant AG) Methylisothiazolinone, Methylparaben, Ethylparaben; 0.8% 0.8% Dipropylene Glycol (Microcare MEM, Thor) Undecylenamidopropyitrimonium Methosulfate; Aqua; 1.0% Propylene Glycol (dermosoft ® UTM, Evonik Dr. Straetmans GmbH)

Recipes 2a, 2b and 2c: Aluminium-Free Deodorant Formulation without Antiperspirant Active Ingredients

Recipe 2a 2b 2c Composition from example 3 3.2% 3.2% 3.2% C18-C22 Hydroxyalkyl Hydroxypropyl Guar (ESAFLOR 0.15%  HM 22, Lamberti S.p.A.) Hydroxypropyl Guar (ESAFLOR HDR, Lamberti S.p.A.) 0.15%  0.15%  Polyglyceryl-3 Caprylate (TEGO ® Cosmo P 813, Evonik 0.5% 0.5% 0.5% Operations GmbH) Zinc Ricinoleate (TEGODEO ® PY 88 G, Evonik 1.0% 1.0% 1.0% Operations GmbH) Caprylic/Capric Triglyceride (TEGOSOFT ® CT, Evonik 5.65%  5.65%  5.65%  Operations GmbH) Water ad 100% ad 100% ad 100% Glycerin 3.0% 3.0% 3.0% Benzyl Alcohol, Benzoic Acid, Sorbic Acid (Rokonsal 1.0% 1.0% 1.0% BSB-N, Ashland Specialty Ingredients) Citric Acid (50% aq.) q.s. q.s. q.s. Pentylene Giycoi (dermosoft ® Pentiol eco, Evonik Dr. 4.0 Straetmans GmbH)

Recipes 3a, 3b and 3c: O/W Deodorant Emulsion Containing Potassium Alum

Recipe 3a 3b 3c Composition from example 3 4.8% 4.8% 4.8% C18-C22 Hydroxyalkyl Hydroxypropyl 0.25%  Guar (ESAFLOR HM 22, Lamberts S.p.A.) Hydroxypropyl Guar (ESAFLOR HDR, 0.25%  0.25%  Lamberts S.p.A.) Isopropyl Palmitate (TEGOSOFT ® P, 5.0% 5.0% 5.0% Evonik Operations GmbH) Water ad 100% ad 100% ad 100% Glycerin 3.0% 3.0% 3.0% Potassium alum 5.0% 5.0% 5.0% Methylisothiazolinone, Methylparaben, 0.8% 0.8% Ethylparaben; Dipropylene Glycol (Microcare MEM, Thor) Pentylene Glycol (dermosoft ® Pentiol 3.5% eco, Evonik Dr. Straetmans GmbH

Recipes 4a and 4b: Antiperspirant/Deodorant Lotion

Recipe 4a 4b Composition from example 3 3.0% 3.0% Diethylhexyl Carbonate (TEGOSOFT ® DEC, Evonik Operations 3.0% 3.0% GmbH) PPG-14 Butyl Ether (TEGOSOFT ® PBE, Evonik Operations 3.0% 3.0% GmbH) Polyglycery-3 Caprylate (TEGO ® Cosmo P813, Evonik 0.5% 0.5% Operations GmbH) Demineralized water ad 100% ad 100% Hydroxyethylcellulose (Natrosol 250 HHR, Ashland Specialty 1.0% 1.0% Chemicals) Aluminium Chlorohydrate (50%) (Reach 501L, Reheis) 15.0%  15.0%  Methylisothiazolinone, Methylparaben, Ethylparaben; Dipropylene 0.8% 3.0% Glycol (Microcare MEM, Thor) 1,2-Hexanediol (dermosoft ® Hexiol, Evonik Dr. Straetmans 2.8% GmbH)

Recipes 5a, 5b and 5c: Antiperspirant/Deodorant Creams

Recipe 5a 5b 5c Composition from example 3 3.0% 2.5% 2.5% Sodium Cetearyl Sulfate (Lanette E, BASF SE) 0.5% 0.5% Glyceryl Stearate 1.0% 1.0% 1.0% Stearyl Alcohol 1.0% 1.0% 1.0% PPG-15 Stearyl Ether 5.0% 5.0% 5.0% Isoamyl Cocoate (TEGOSOFT ® AC, Evonik Operations 5.0% 5.0% 5.0% GmbH) Diethylhexyl Carbonate (TEGOSOFT ® DEC, Evonik 5.0% 5.0% 5.0% Operations GmbH) Persea Gratissima (avocado) Oil 2.0% 2.0% 2.0% Polyglycery-3 Caprylate (TEGO ® Cosmo P813, Evonik 0.5% 0.5% 0.5% Operations GmbH) Zinc Ricinoleate (TEGODEO ® PY88 G, Evonik 1.0% 1.0% 1.0% Operations GmbH) Demineralized water ad 100% ad 100% ad 100% Hydroxyethylcellulose (Natrosol 250 HHR (Ashland 1.0% 1.0% 1.0% Specialty Chemicals) Aluminium Chlorohydrate (50% aq.; Locron LIC, Clariant 15.0%  15.0%  15.0%  AG) Methylisothiazolinone, Methylparaben, Ethylparaben: 0.8% 0.8% Dipropylene Glycol (Microcare MEM, Thor) Methylpropanediol; Caprylyl Glycol; Phenylpropanol 3.5% (dermosoft ® OMP; Evonik Dr. Straetmans GmbH)

Recipes 6a and 6b: Sun Care Spray SPF 30

Recipe 6a 6b Composition from example 3 4.0% 4.0% Phenoxyethyl Caprylate (TEGOSOFT ® XC, Evonik Operations 3.2% 3.2% GmbH) Isopropyl Palmitate (TEGOSOFT ® P, Evonik Operations GmbH) 2.0% 2.0% Bis-Ethylhexyloxyphenol Methoxyphenyl Triazine (Tinosorb S, 3.0% 3.0% BASF SE) Butyl Methoxydibenzoylmethane 2.0% 2.0% EHC 2.0% 2.0% Ethylhexyl Salicylate 4.0% 4.0% Octocrylene 4.0% 4.0% Glycerin 3.0% 3.0% Water ad 100% ad 100% Carbomer suspension 1 (Acrylates/C10-30 Alkyl Acrylate 1.0% 1.0% Crosspolymer, TEGO ® Carbomer 341ER, Evonik Operations GmbH, 20% in Phenoxyethyl Caprylate) Tris(hydroxymethyl)aminomethane (30% aq.) 0.6% 0.6% UV filter solution (20% Phenylbenzimidazole Sulfonic Acid, 8.8% 10.0%  10.0%  tris(hydroxymethyf)aminomethane, demineralized water to 100%) Methylisothiazolinone, Methylparaben, Ethylparaben; Dipropylene 0.8% Glycol (Microcare MEM, Thor) Methylpropanediol; Caprylyl Glycol (dermosoft ® OM, Evonik Dr. 4.0 Straetmans GmbH)

Recipes 7a, 7b and 7c: Sunscreen Spray

Recipe 7a 7b 7c Composition from example 3 3.0% 2.5% 2.5% Glyceryl Stearate Citrate (AXOL ® C 62, Evonik Operations GmbH) 0.5% 0.5% Glyceryl Stearate 0.5% 0.5% 0.5% Stearyl Alcohol 0.5% 0.5% 0.5% Bis-Ethythexyloxyphenol Methoxyphenyl Triazine (Tinosorb S, BASF 3.0% 3.0% 3.0% SE) Butyl Methoxydibenzoylmethane 2.0% 2.0% 2.0% Ethylhexyl Methoxycinnamate 2.0% 2.0% 2.0% Ethylhexyl Salicylate 4.0% 4.0% 4.0% Octocrylene 4.0% 4.0% 4.0% Isopropyl Palmitate 2.0% 2.0% 2.0% Phenoxyethyl Caprylate (TEGOSOFT ® XC, Evonik Operations GmbH) 3.2% 3.2% 3.2% Glycerin 3.0% 3.0% 3.0% Demineralized water ad 100% ad 100% ad 100% Carbomer suspension (Acrylates/C10-30 Alkyl Acrylate Crosspolymer, 1.0% 1.0% 1.0% TEGO ® Carbomer 341ER, 20% in Phenoxyethyl Caprylate) Tromethamine (30%) 0.9% 0.9% 0.9% UV filter solution (20% Phenylbenzimidazole Sulfonic Acid, 8.8% 10.0%  10.0%  10.0%  tris(hydroxymethyl)aminomethane, demineralized water to 100%) Methylisothiazolinone, Methylparaben, Ethylparaben; Dipropylene Glycol 0.8% 0.8% (Microcare MEM, Thor) Methylpropanediol; Caprylyl Glycol; Phenylpropanol (dermosoft ® OMP; 3.0% Evonik Dr. Straetmans GmbH)

Recipes 8a, 8b and 8c: Sunscreen Lotion, SPF 30

Recipe 8a 8b 8c Composition from exampie 3 3.00% 2.00% 2.00% Cetearyl Glucoside (TEGO ® Care CG 90, Evonik 0.50% 0.50% Operations GmbH) Phenoxyethyl Caprylate (TEGOSOFT ® XC, Evonik 8.00% 8.00% 8.00% Operations GmbH) Diethylamino Hydroxybenzoyl Hexyl Benzoate (Uvinul A 6.00% 6.00% 6.00% Pius, BASF SE) Ethylhexyl Methoxycinnamate 8.00% 8.00% 8.00% Stearyl Alcohol 1.00% 1.00% 1.00% Glyceryl Stearate 1.00% 1.00% 1.00% Tocopheryl Acetate 0.50% 0.50% 0.50% Glycerin 2.00% 2.00% 2.00% Demineralized water ad 100% ad 100% ad 100% Tromethamine 0.90% 0.90% 0.90% Phenylbenzimidazole Sulfonic Acid 2.00% 2.00% 2.00% Acrylates/C10-30 Alkyl Acrylate Crosspolymer (TEGO ® 0.30% 0.30% 0.30% Carbomer 341 ER, Evonik Operations GmbH) Sodium hydroxide (10% aq.) q.s. q.s. q.s. Methylisothiazolinone, Methylparaben, Ethylparaben; 0.80% 0.80% Dipropylene Glycol (Microcare MEM, Thor) Caprylyl Glycol; Glycerin; Glyceryl Caprylate: 1.0 Phenylpropanol; Aqua (dermosoft ® LP MB; Evonik Dr. Straetmans GmbH)

Recipes 9a, 9b and 9c: Sunscreen Lotion SPF 30, High UVA Protection

Recipe 9a 9b 9c Composition from exampie 3 3.00% 2.50% 2.50% Sodium Cetearyl Sulfate (Lanette E, BASF SE) 0.50% 0.50% Phenoxyethyl Caprylate (TEGOSOFT ® XC, Evonik 7.30% 7.30% 7.30% Operations GmbH) Butyl Methoxydibenzoylmethane 5.00% 5.00% 5.00% Diethylhexyl Butamido Triazone (UVAsorb HEB, 3V 1.00% 1.00% 1.00% Sigma) Ethylhexyl Salicylate 1.50% 1.50% 1.50% Octocrylene 3.50% 3.50% 3.50% Titanium Dioxide; Diethylhexyl Carbonate; Polyglyceryl-6 2.20% 2.20% 2.20% Polyhydroxystearate (TEGO ® Sun TDEC 45, Evonik Operations GmbH) Stearyl Alcohol 1.00% 1.00% 1.00% Nylon-10/10 (TEGOLON ® ECO 10-10, Evonik Operations 0.50% 0.50% 0.50% GmbH) Glyceryl Stearate 1.00% 1.00% 1.00% Tocopheryl Acetate 0.50% 0.50% 0.50% Glycerin 2.00% 2.00% 2.00% Demineralized water ad 100% ad 100% ad 100% Citric Acid (50% aq.) 0.10% 0.10% 0.10% Bis-Ethylhexyloxyphenol Methoxyphenyl Triazine 20.00%  20.00%  20.00%  (Tinosorb S, BASF SE) Acrylates/C10-30 Alkyl Acrylate Crosspolymer (TEGO ® 0.30% 0.30% 0.30% Carbomer 341 ER, Evonik Operations GmbH) Sodium Hydroxide (10% aq.) 0.90% 0.90% 0.90% Methylisothiazolinone, Methylparaben, Ethylparaben; 0.80% 0.80% Dipropylene Glycol (Microcare MEM. Thor) Triethyl Citrate; Caprylyl Glycol; Benzoic Acid (Verstatil ®  1.0% TBO; Evonik Dr. Straetmans GmbH)

Recipes 10a, 10b and 10c: Sunscreen Lotion, SPF 30

Recipe 10a 10b 10c Composition from exampie 3 3.00% 2.00% 2.00% Methyl Glucose Sesquistearate (TEGO ® Care PS, 1.00% 1.00% Evonik Operations GmbH) Phenoxyethyl Caprylate (TEGOSOFT ® XC, Evonik 1.50% 1.50% 1.50% Operations GmbH) Octocrylene 10.00%  10.00%  10.00%  Butyl Methoxydibenzoylmethane 3.50% 3.50% 3.50% Titanium Dioxide; Diethylhexyl Carbonate; 14.50%  14.50%  14.50%  Polyglycery-6 Polyhydroxystearate (TEGO ® Sun TDEC 45, Evonik Operations GmbH) Stearyl Alcohol 0.20% 0.20% 0.20% Glyceryl Stearate 0.20% 0.20% 0.20% Tocopheryl Acetate 0.50% 0.50% 0.50% Glycerin 2.00% 2.00% 2.00% Demineralized water ad 100% ad 100% ad 100% Acry lates/C10-30 Alkyl Acrylate Crosspolymer 0.20% 0.20% 0.20% (TEGO ® Carbomer 341 ER, Evonik Operations GmbH) Sodium Hydroxide (10% aq.) 0.60% 0.60% 0.60% Methylisothiazolinone, Methylparaben, Ethylparaben; 0.80% 0.80% Dipropylene Glycol (Microcare MEM, Thor) Methylpropanediol; Caprylyl Glycol; Phenylpropanol 3.0% (dermosoft ® OMP; Evonik Dr. Straetmans GmbH)

Recipes 11a, 11b and 11c: Sunscreen Lotion SPF 50, High UVA Protection

Recipe 11a 11b 11c Composition from example 3 3.00% 2.50% 2.50% Polyglycery-3 Methylglucose Distearate (TEGO ® Care 450, 0.50% 0.50% Evonik Operations GmbH) Phenoxyethyl Caprylate (TEGOSOFT ® XC, Evonik 2.00% 2.00% 2.00% Operations GmbH) Nylon-10/10 (TEGOLON ® ECO 10-10, Evonik 0.50% 0.50% 0.50% Operations GmbH) Butyl Methoxydibenzoylmethane 5.00% 5.00% 5.00% Diethylhexyl Butamido Triazone (UVAsorb HEB, 3V Sigma) 1.00% 1.00% 1.00% Bis-Ethylhexyloxyphenol Methoxyphenyl Triazine 3.00% 3.00% 3.00% (Tinosorb S, BASF SE) Ethylhexyl Salicylate 1.00% 1.00% 1.00% Octocrylene 8.00% 8.00% 8.00% Stearyi Alcohol 0.45% 0.45% 0.45% Glyceryl Stearate 0.45% 0.45% 0.45% Xanthan Gum (Keltrol CG-SFT, CP Kelco) 0.30% 0.30% 0.30% Tocopheryl Acetate 0.50% 0.50% 0.50% Hydroxyethylcellulose (Natrosol 250 HHR (Ashland 0.50% 0.50% 0.50% Specialty Chemicals) Demineralized water ad 100% ad 100% ad 100% Sodium Hydroxide (10% aq., pH adjustment to 7.5) q.s. q.s. q.s. Disodium Phenyl Dibenzimidazole Tetrasulfonate 5.00% 5.00% 5.00% (Neoheliopan AP, Symrise) Methylene Bis-Benzotriazolyl Tetramethylbutyiphenol 8.00% 8.00% 8.00% (Tinosorb M, BASF SE) Methylisothiazolinone, Methylparaben, Ethylparaben; 0.80% 0.80% Dipropylene Glycol (Microcare MEM, Thor) Methylpropanediol; Caprylyl Glycol (dermosoft ® OM,  3.8% Evonik Dr. Straetmans GmbH)

Recipes 12a, 12b and 12c: Sunscreen Lotion, SPF 50

Recipe 12a 12b 12c Composition from example 3 3.50% 3.00% 3.00% Glyceryl Stearate Citrate (AXOL ® C 62, 1.00% 1.00% Evonik Operations GmbH) Phenoxyethyl Caprylate (TEGOSOFT ® 2.50% 2.50% 2.50% XC, Evonik Operations GmbH) Diethylamino Hydroxybenzoyl, 10.00%  10.00%  10.00%  Hexyl Benzoate Ethylhexyl Methoxycinnamate 10.00%  10.00%  10.00%  Stearyl Alcohol 1.00% 1.00% 1.00% Glyceryl Stearate 1.00% 1.00% 1.00% Xanthan Gum (Keltrol CG-SFT, CP Kelco) 0.50% 0.50% 0.50% Tocopheryl Acetate 0.50% 0.50% 0.50% Glycerin 2.00% 2.00% 2.00% Demineralized water ad ad ad  100%  100%  100% Phenylbenzimidazole Sulfonic Acid 4.00% 4.00% 4.00% Tromethamine 1.80% 1.80% 1.80% Methylisothiazolinone, Methylparaben, 0.80% 0.80% Ethylparaben; Dipropylene Glycol (Microcare MEM, Thor) Triethyl Citrate; Glyceryl Caprylate;  1.2% Benzoic Acid (Verstatil ® TBG MB, Evonik Dr. Straetmans GmbH)

Recipes 13a, 13b and 13c: Sunscreen Lotion SPF 50+

Recipe 13a 13b 13c Composition from example 3 3.00%  2.5%  2.5% Potassium Cetyl Phosphate  1.0%  1.0% Phenoxyethyl Caprylate (TEGOSOFT ® 3.00% 3.00% 3.00% XC, Evonik Operations GmbH) Butyl Methoxydibenzoylmethane 5.00% 5.00% 5.00% Octocrylene 4.90% 4.90% 4.90% Ethylhexyl Methoxycinnamate 0.10% 0.10% 0.10% Bis-Ethylhexyloxyphenol Methoxyphenyl 4.70% 4.70% 4.70% Triazine (Tinosorb S, BASF SE) Diethylhexyl Butamido Triazone (UVAsorb 3.70% 3.70% 3.70% HEB, 3 V Sigma) Titanium Dioxide; Diethylhexyl Carbonate; 11.00%  11.00%  11.00%  Polyglyceryl-6 Polyhydroxystearate (TEGO ® Sun TDEC 45, Evonik Operations GmbH) Stearyl Alcohol 0.50% 0.50% 0.50% Glyceryl Stearate 0.50% 0.50% 0.50% Xanthan Gum (Keltrol CG-SFT, 0.20% 0.20% 0.20% CP Kelco) Glycerin 2.00% 2.00% 2.00% Demineralized water ad ad ad  100%  100%  100% Methylisothiazolinone, Methylparaben, 0.80% 0.80% Ethylparaben; Dipropylene Glycol (Microcare MEM, Thor) Triethyl Citrate; Caprylyl Glycol;  0.9% Benzoic Acid (Verstatil ® TBO; Evonik Dr. Straetmans GmbH)

Recipes 14a and 14b: Body Lotion

Recipe 14a 14b Composition from example 3 4.0% 4.0% Isoamyl Cocoate (TEGOSOFT ® AC, 2.5% 2.5% Evonik Operations GmbH) Caprylic/Capric Triglyceride (TEGOSOFT ® 3.5% 3.5% CT, Evonik Operations GmbH) Water ad ad 100%  100%  Creatine (TEGO ® Cosmo C 100, 0.5% 0.5% Evonik Operations GmbH) Carbomer suspension 2 (Carbomer, TEGO ® 1.0% 1.0% Carbomer 141, Evonik Operations GmbH, 20% in Ethylhexyl Stearate) Sodium Hydroxide (10% aq.) 0.6% 0.6% Phenoxyethanol, Ethylhexylglycerin (Euxyl 0.7% PE 9010, Schülke & Mayr GmbH) Aqua; Sodium Levulinate; Sodium Benzoate 1.5% (Verstatil ® BL; Evonik Dr. Straetmans GmbH) Glyceryl Caprylate (dermosoft ® GMCY MB; 0.3% Evonik Dr. Straetmans GmbH)

Recipes 15a and 15b: Natural Care Cream

Recipe 15a 15b Composition from example 3 6.0% 6.0% Caprylic/Capric Triglyceride (TEGOSOFT ® 8.0% 8.0% CT, Evonik Operations GmbH) Isopropyl Palmitate (TEGOSOFT ® P, 11.0%  11.0%  Evonik Operations GmbH) Prunus Amygdalus Dulcis (sweet almond) Oil 10.0%  10.0%  Water ad ad 100%  100%  Glycerin 3.0% 3.0% Sodium Hydroxide (10% aq.) 0.2% 0.2% Benzyl Alcohol, Benzoic Acid, Sorbic 0.8% Acid (Rokonsal BSB-N, Ashland Specialty Ingredients) Glycerin; Aqua; Sodium Levulinate;   3% Sodium Anisate (dermosoft ® 1388 eco; Evonik Dr. Straetmans GmbH) Glyceryl Caprylate (dermosoft ® GMCY 0.2% MB; Evonik Dr. Straetmans GmbH)

Recipes 16a and 16b: Anti-Ageing Cream

Recipe 16a 16b Composition from example 3 6.0% 6.0% Caprylic/Capric Triglyceride (TEGOSOFT ® CT, Evonik Operations 9.5% 9.5% GmbH) C12-15 Alkyl Benzoate (TEGOSOFT ® TN, Evonik Operations 9.5% 9.5% GmbH) Water ad ad 100%  100%  Glycerin 3.0% 3.0% Tetrapeptide-21; Glycerin; Butylene Glycol; Aqua (TEGO ® 4.0% 4.0% Pep 4-17, Evonik Operations GmbH) Sodium Hyaluronate (HyaCare ®, Evonik Operations GmbH) 0.1% 0.1% Hydrolyzed Hyaluronic Acid (HyaCare ® 50, Evonik Operations 0.1% 0.1% GmbH) Aqua: Ethylhexyl Stearate; Sodium Hyaluronate Crosspolymer; 5.0% 5.0% Polyglyceryl-4 Diisostearate/Polyhydroxystearate/Sebacate; Sodium Isostearate (HyaCare ® Filler CL, Evonik Operations GmbH) Methylisothiazolinone, Methylparaben, Ethylparaben; Dipropylene 0.8% Glycol (Microcare MEM, Thor) Aqua; Sodium Levulinate; Potassium Sorbate (Verstatil SL non 1.2% GMO; Evonik Dr. Straetmans GmbH) Caprylyl Glycol (dermosoft ® Octiol; Evonik Dr. Straetmans GmbH) 0.2%

Recipes 17a and 17b: O/W Foundation

Recipe 17a 17b Composition from example 3 6.0% 6.0% Myristyl Myristate (TEGOSOFT ® MM, 2.0% 2.0% Evonik Operations GmbH) Isopropyl Myristate (TEGOSOFT ® M, 6.0% 6.0% Evonik Operations GmbH) Decyl Cocoale (TEGOSOFT ® DC, 6.0% 6.0% Evonik Operations GmbH) Cetyl Ricinoleate (TEGOSOFT ® CR, 1.0% 1.0% Evonik Operations GmbH) Water ad ad 100%  100%  Glycerin 1.0% 1.0% Titanium Dioxide (Hombitan AC 360, 8.0% 8.0% Sachtleben) Iron Oxides (Sicovit Yellow 10 E 172, 0.9% 0.9% Rockwood Pigments) Iron Oxides (Sicovit Red 30 E 172, 0.2% 0.2% Rockwood Pigments) Iron Oxides (Sicovit Brown 70 E 172, 0.4% 0.4% Rockwood Pigments) Iron Oxides (Sicovit Black 80 E 172, 0.1% 0.1% Rockwood Pigments) Cellulose (TEGO ® Feel Green, 2.0% 2.0% Evonik Operations GmbH) Sodium Hydroxide (10% aq.) 0.2% 0.2% Benzyl Alcohol, Benzoic Acid, 1.0% Sorbic Acid (Rokonsal BSB-N, Ashland Specialty Ingredients) Methylpropanediol; Caprylyl Glycol: 3.2% Phenylpropanol (dermosoft ® OMP; Evonik Dr. Straetmans GmbH)

Recipes 18a, 18b, 18c and 18d: Lotions with Cosmetic Active Ingredients

Recipe 18a 18b 18c 18d Composition from example 3 3.5% 3.5% 3.0% 3.0% Stearic Acid 0.5% 0.5% Glyceryl Stearate 0.5% 0.6% 0.6% 0.6% Cetearyl Alcohol 0.5% 0.6% 0.6% 0.6% Caprylic/Capric Triglyceride 8.5% 8.5% 8.5% 8.5% Ethylhexyl Palmitate 8.5% 8.5% 8.5% 8.5% (TEGOSOFT ® OP, Evonik Operations GmbH) Demineralized water ad ad ad ad 100%  100%  100%  100%  Xanthan Gum (Keltrol CG-SFT, 0.8% 0.8% 0.8% 0.8% CP Kelco) Terminalia Arjuna Bark Extract; 2.0% 2.0% 2.0% Pentylene Glycol (proposed; TEGO ® Arjuna S, Evonik Operations GmbH) Betaine; Urea; Potassium 5.0% Lactate; Sodium Polyglutamate (proposed); Hydrolyzed Sclerotium Gum (TEGO ® Smooth; Evonik Operations GmbH) Phenoxyethanol, 1.0% Methylparaben, Ethylparaben, Propylparaben (Phenonip XB (Clariant International Ltd.) Methylisothiazolinone, 0.8% 0.8% Methylparaben, Ethylparaben; Dipropylene Glycol (Microcare MEM, Thor) Caprylyl Glycol; Glyceryl 1.0% Caprylate; Dipropylene Glycol (dermosoft ® MCAV MB; Evonik Dr. Straetmans GmbH)

Recipes 19a, 19b and 19c: Lotion with Low Oil Phase Content

Recipe 19a 19b 19c Composition from example 3 3.0% 2.0% 2.0% Polyglyceryl-3 Dicitrate/Stearate (TEGO ® Care PSC 3 1.0% 1.0% (Evonik Operations GmbH) Cetearyl Alcohol 0.5% 0.5% 0.5% Caprylic/Capric Triglyceride 6.5% 6.5% 6.5% Demineralized water ad ad ad 100%  100%  100%  Xanthan Gum (Keltrol CG-SFT, CP Kelco) 0.5% 0.5% 0.5% Methylisothiazolinone, Methylparaben, Ethylparaben; 0.8% 0.8% Dipropylene Glycol (Microcare MEM, Thor) Glycerin; Aqua; Sodium Levulinate; Sodium Anisate 3.0% (dermosoft ® 1388; Evonik Dr. Straetmans GmbH)

Recipes 20a, 20b 20c and 20d: O/W Serums 1

Recipe 20a 20b 20c 20d Composition from example 3 2.5% 2.5% 4.0% 4.0% Sodium Stearoyl Glutamate (Eumulgin SG, 1.0% BASF SE) Glyceryl Stearate 0.75%  0.75%  Stearyl Alcohol 0.75%  0.75%  Caprylic/Capric Triglyceride 2.0% 2.0% 2.0% 2.0% Oleyl Erucate (TEGOSOFT ® OER, Evonik 2.0% 2.0% 2.0% 2.0% Operations GmbH) Isoamyl Cocoate (TEGOSOFT ® AC, Evonik 3.0% 3.0% Operations GmbH) Persea Gratissima (avocado) Oil 1.0% 1.0% 1.0% 1.0% Aqua; Ethylhexyl Stearate; Sodium Hyaluronate 3.0% 3.0% Crosspolymer; Polyglycery/-4 Diisostearate/Polyhydroxystearate/Sebacate; Sodium Isostearate (HyaCare ® Filler CL, Evonik Operations GmbH) Demineralized water ad ad ad ad 100%  100%  100%  100%  Butylene Glycol 5.0% 5.0% 5.0% 5.0% Tetrapeptide-21; Glycerin; Butylene Glycol; Aqua 2.0% 2.0% 2.0% 2.0% (TEGO ® Pep 4-17, Evonik Operations GmbH) Hydrolyzed Hyaluronic Acid (HyaCare ® 50, 0.1% 0.1% 0.1% 0.1% Evonik Operations GmbH) Xanthan Gum (Keltrol CG-SFT, CP Kelco) 0.5% 0.5% 0.5% 0.5% Sodium Hydroxide (10% aq.) 0.2% 0.2% 0.2% 0.2% Benzyl Alcohol, Benzoic Acid, Sorbic Acid 0.8% 0.8% 0.8% (Rokonsal BSB-N, Ashland Specialty Ingredients) Polyglutamic Acid; Sclerotium glucan; Betaine; 3.0% 3.0% 3.0% 3.0% Urea; Potassium Lactate (TEGO ® Smooth Complex, Evonik Operations GmbH) Triethyl Citrate; Glyceryl Caprylate; Benzoic Acid 1.2% (Verstatil ® TBG; Evonik Dr. Straetmans GmbH)

Recipes 20e, 20f, 20g and 20h: O/W Serums 2

Recipe 20e 20f 20g 20h Composition from example 3 3.0% 3.0% 2.0% 2.0% Cetearyl Glucoside (TEGO ® Care CG 90, Evonik 0.5% Operations GmbH) Polyglycery-3 Dicitrate/Stearate (TEGO ® Care PSC 3, 1.5% 1.5% Evonik Operations GmbH) Glyceryl Stearate 0.75%  0.5% 0.5% 0.5% Stearyl Alcohol 0.75%  0.5% 0.5% 0.5% Caprylic/Capric Triglyceride 2.0% 2.0% 2.0% 2.0% Oleyl Erucate (TEGOSOFT ® OER, Evonik Operations 2.0% 2.0% 2.0% 2.0% GmbH) Isoamyl Cocoate (TEGOSOFT ® AC, Evonik Operations 3.0% GmbH) Persea Gratissima (avocado) Oil 1.0% 1.0% 1.0% 1.0% Aqua; Ethylhexyl Stearate; Sodium Hyaluronate 3.0% 3.0% 3.0% Crosspolymer; Polyglycery/-4 Diisostearate/Polyhydroxystearate/Sebacate; Sodium Isostearate (HyaCare ® Filler CL, Evonik Operations GmbH) Demineralized water ad ad ad ad 100%  100%  100%  100%  Butylene Glycol 5.0% 5.0% 5.0% 5.0% Tetrapeptide-21; Glycerin; Butylene Glycol; Aqua 2.0% 2.0% 2.0% 2.0% (TEGO ® Pep 4-17, Evonik Operations GmbH) Hydrolyzed Hyaluronic Acid (HyaCare ® 50, Evonik 0.1% 0.1% 0.1% 0.1% Operations GmbH) Xanthan Gum (Keltrol CG-SFT, CP Kelco) 0.5% 0.5% 0.5% 0.5% Sodium Hydroxide (10% aq.) 0.2% 0.2% 0.2% 0.2% Benzyl Alcohol, Benzoic Acid, Sorbic Acid (Rokonsal 0.8% 0.8% 0.8% BSB-N, Ashland Specialty Ingredients) Polyglutamic Acid; Sclerotium glucan; Betaine; 3.0% 3.0% Urea; Potassium Lactate (TEGO ® Smooth Complex, Evonik Operations GmbH) Triethyl Citrate; Caprylyl Glycol; Benzoic Acid (Verstatil ® 1.0% TBO; Evonik Dr. Straetmans GmbH)

Recipes 21a, 21b and 21c: O/W Blemish Balm Lotion

Recipe 21a 21b 21c Composition from example 3 4.00% 3.00% 3.00% Polyglycery-3 Methylglucose Distearate (TEGO ® Care 450, 1.00% 1.00% Evonik Operations GmbH) Glyceryl Stearate 0.75% 0.75% 0.75% Stearyl Alcohol 0.75% 0.75% 0.75% Diethylhexyl Carbonate (TEGOSOFT ® DEC, Evonik 7.40% 7.40% 7.40% Operations GmbH) Aqua; Ethylhexyl Stearate; Sodium Hyaluronate Crosspolymer; 2.00% 2.00% 2.00% Polyglyceryl-4 Diisostearate/Polyhydroxystearate/Sebacate; Sodium isostearate (HyaCare ® Filler CL, Evonik Operations GmbH) Ethylhexyl Methoxycinnamate 5.00% 5.00% 5.00% Diethylamino Hydroxybenzoyl Hexyl Benzoate (Uvinul A Plus, 3.00% 3.00% 3.00% BASF SE) Phytosphingosine 0.10% 0.10% 0.10% Hydrolyzed Hyaluronic Acid (HyaCare ® 50, Evonik Operations 0.10% 0.10% 0.10% GmbH) Tetrapeptide-21; Glycerin; Butylene Glycol; Aqua (TEGO ® 2.00% 2.00% 2.00% Pep 4-17, Evonik Operations GmbH) Demineralized water ad ad ad  100%  100%   100% Titanium Dioxide (Hombitan AC 360, Sachtleben) 3.00% 3.00% 3.00% Talc 2.00% 2.00% 2.00% Iron Oxide (Unipure Yellow LC 182, Sensient Technologies) 0.36% 0.36% 0.36% Iron Oxide (Unipure Red LC 381, Sensient Technologies) 0.12% 0.12% 0.12% Iron Oxide (Unipure Black LC 989, Sensient Technologies) 0.08% 0.08% 0.08% Isoamyl Cocoale (TEGOSOFT ® AC, Evonik Operations GmbH) 4.44% 4.44% 4.44% Phenoxyethyl Caprylate (TEGOSOFT ® XC, Evonik Operations 4.00% 4.00% 4.00% GmbH) Nylon-10/10 (TEGOLON ® ECO 10-10, Evonik Operations 3.00% 3.00% 3.00% GmbH) Glycerin 3.00% 3.00% 3.00% Xanthan Gum (Keltrol CG-SFT, CP Kelco) 0.50% 0.50% 0.50% Ethanol 3.00% 3.00% 3.00% Methylisothiazolinone, Methylparaben, Ethylparaben; 0.80% 0.80% Dipropylene Glycol (Microcare MEM, Thor) Methylpropanediol; Caprylyl Glycol (dermosoft ® OM, Evonik  4.0% Dr. Straetmans GmbH)

Recipes 22a, 22b, 22c and 22d: Lotion for Sensitive Skin

Recipe 22a 22b 22c 22d Composition from example 3 3.0% 3.0% 3.0% 3.0% Glyceryl Stearate 0.5% 1.0% 0.5% 0.5% Cetearyl Alcohol 1.0% 1.0% 1.0% 1.0% Butyrospermum Parkii Butter (shea butter) 3.0% 3.0% 3.0% 3.0% Caprylic/Capric Triglyceride 5.0% 5.0% 5.0% 5.0% Isopropyl Palmitate (TEGOSOFT ® P, Evonik Operations GmbH) 5.0% 5.0% 5.0% 5.0% Xanthan Gum (Keltrol CG-SFT, CP Kelco) 0.2% 0.2% 0.2% 0.2% Glycerin 5.0% 5.0% 5.0% 5.0% Urea 10.0%  15.0%  20.0%  20.0%  Demineralized water ad ad ad ad 100%  100%  100%  100%  Phenoxyethanol, Ethylhexylglycerin (Euxyl PE 9010, Schülke & 0.7% Mayr GmbH) Sodium Hydroxide (10% aq.) (pH adjustment to 5.0) q.s. Sodium Benzoate, Potassium Sorbate (Euxyl K 712, Schülke & 1.2% Mayr GmbH) Methylisothiazolinone, Methylparaben, Ethylparaben; 0.8% Dipropylene Glycol (Microcare MEM, Thor) Sodium Anisate (dermosoft ® anisate; Evonik Dr. Straetmans 0.12%  GmbH) Levulinic Acid; Sodium Levulinate; Glycerin: Aqua (dermosoft ® 1.0% 700B; Evonik Dr. Straetmans GmbH) Glyceryl Caprylate (dermosoft ® GMC MB; Evonik Dr. 0.3% Straetmans GmbH)

Recipes 23a, 23b, 23c and 23d: Care Lotion for Dry Skin

Recipe 23a 23b 23c 23d Composition from example 3 3.0% 2.5% 3.0% 3.0% Sodium Stearoyl Glutamate (Eumulgin SG, BASF SE) 1.0% Glyceryl Stearate 1.0% 1.0% 1.5% 1.5% Cetearyl Alcohol 1.0% 1.0% 1.5% 1.5% Cetyl Ricinoleate 2.0% 2.0% 2.0% 2.0% Oleyl Erucate (TEGOSOFT ® OER, Evonik Operations GmbH) 5.0% 5.0% 5.0% 5.0% Isoamyl Cocoate (TEGOSOFT ® AC, Evonik Operations GmbH) 8.0% 8.0% 8.0% 8.0% Decyl Cocoate (TEGOSOFT ® DC, Evonik Operations GmbH) 3.0% 3.0% 3.0% 3.0% Xanthan Gum (Keltrol CG-SFT, CP Kelco) 0.2% 0.2% 0.2% 0.2% Glycerin 5.0% 5.0% 5.0% 5.0% Urea 10.0%  10.0%  15.0%  15.0%  Demineralized water ad ad ad ad 100%  100%  100%  100%  Methylisothiazolinone, Methylparaben, Ethylparaben; 0.8% 0.8% 0.8% Dipropylene Glycol (Microcare MEM, Thor) Phenethyl Alcohol (dermosoft ® PEA; Evonik Dr. Straetmans 1.0% GmbH)

Recipes 23e, 23f, 23g and 23h: Care Lotion for Dry Skin 2

Recipe 23e 23f 23g 23h Composition from example 3 2.5% 3.0% 3.0% 3.0% Polyglyceryl-6 Distearate 0.5% Stearic Acid 0.5% 0.5% Glyceryl Stearate 1.5% 1.5% 1.5% 1.5% Cetearyl Alcohol 1.5% 1.5% 1.5% 1.5% Cetyl Ricinoleate 2.0% 2.0% 2.0% 2.0% Oleyl Erucate (TEGOSOFT ® OER, Evonik Operations GmbH) 5.0% 5.0% 5.0% 5.0% Isoamyl Cocoate (TEGOSOFT ® AC, Evonik Operations GmbH) 8.0% 8.0% 8.0% 8.0% Decyl Cocoate (TEGOSOFT ® DC, Evonik Operations GmbH) 3.0% 3.0% 3.0% 3.0% Xanthan Gum (Keltrol CG-SFT, CP Kelco) 0.2% 0.2% 0.2% 0.2% Glycerin 5.0% 5.0% 5.0% 5.0% Urea 15.0%  20.0%  20.0%  20.0%  Demineralized water ad ad ad ad 100%  100%  100%  100%  Methylisothiazolinone, Methylparaben, Ethylparaben; 0.8% 0.8% 0.8% Dipropylene Glycol (Microcare MEM, Thor) Phenylpropanol (dermosoft ® 250 eco; Evonik Dr. Straetmans 0.4% GmbH) 1,2-Hexanediol (dermosoft ® Hexiol; Evonik Dr. Straetmans 3.0% GmbH)

Recipes 24a, 24b and 24c: Preservative-Free Lotions 1

Recipe 24a 24b 24c Composition from example 3 3.0% 2.0% 3.0% (AXOL ® C 62, Evonik Operations GmbH) 1.0% Glyceryl Stearate 0.2% 0.2% 0.5% Stearyl Alcohol 0.2% 0.2% 0.5% Primus Amygdalus Dulcis (sweet almond) Oil 10.0%  10.0%  10.0%  Isoamyl Cocoate (TEGOSOFT ® AC, Evonik Operations GmbH) 6.6% 6.6% 6.0% Glycerin 4.0% 4.0% 4.0% Demineralized water ad ad ad 100.0%   100.0%   100.0%   Caprylyl Glycol, Glycerin, Glyceryl Caprylate, Phenylpropanol 1.0% 1.0% (Dermosoft ® LP, Evonik Dr, Straetmans GmbH) Methylpropanediol, Caprylyl Glycol, Phenylpropanol 4.0% (Dermosoft ® OMP, Evonik Dr. Straetmans GmbH) Xanthan Gum (Keltrol CG-SFT, CP Kelco) 0.5% 0.5% 0.5%

Recipes 24d, 24e and 24f: Preservative-Free Lotions 2

Recipe 24d 24e 241 Composition from example 3 3.0% 3.0% 1.5% Glyceryl Stearate SE 0.5% Polyglycery-3 Dicitrate/Stearate (TEGO ® Care PSC 3, Evonik 1.5% Operations GmbH) Glyceryl Stearate 0.5% 0.5% 0.5% Stearyl Alcohol 0.5% 0.5% 0.5% Prunus Amygdalus Dulcis (sweet almond) Oil 10.0%  10.0%  10.0%  Isoamyl Cocoate (TEGOSOFT ® AC, Evonik Operations GmbH) 6.0% 6.0% 6.0% Glycerin 4.0% 4.0% 4.0% Demineralized water ad ad ad 100.0%  100.0%  100.0%  Methylpropanediol, Caprylyl Glycol, Phenylpropanol (Dermosoft ® 4.0% OMP, Evonik Dr. Straetmans GmbH) Caprylyl Glycol (Dermosoft ® Octiol, Evonik Dr. Straetmans 0.4% 0.4% GmbH) p-Anisio Acid 10% solution (dissolve 3.0 g of Sodium Hydroxide 2.0% 2.0% in 56.5 g of demineralized water, add 30.0 g of Glycerin and 10.0 g of Dermosoft ® Octiol (Evonik Dr. Straetmans GmbH), and stir until the solution is clear) Citric Acid (10% aq.) (pH adjustment to 6.0) q.s. q.s. Xanthan Gum (Keltrol CG-SFT, CP Kelco) 0.5% 0.5% 0.5%

Recipes 25a and 25b: W/O Lotion

Recipe 25a 25b Composition from example 2 2.0% 2.0% Beeswax 0.5% 0.5% Castor wax 0.5% 0.5% Paraffinum perliquidum 10.5%  10.5%  Decyl Cocoale (TEGOSOFT ® DC, 8.0% 8.0% Evonik Operations GmbH) Tocopheryl Acetate 0.5% 0.5% Cyclopentasiloxane 6.0% 6.0% Sodium Chloride 0.5% 0.5% Water ad ad 100%  100%  Glycerin 3.0% 3.0% Phenoxyethanol; Ethylhexylglycerin 0.7% (Euxyl PE 9010, Schülke & Mayr GmbH) Ethanol 5.0% 5.0% Glyceryl Caprylate (dermosoft ® GMC; 0.4% Evonik Dr. Straetmans GmbH) Zinc Sulfate 1.0%

Recipes 26a and 26b: W/O Cream

Recipe 26a 26b Composition from example 2  2.0%  2.0% Mineral oil 17.0% 17.0% Castor wax  0.4%  0.4% Microcrystalline Wax  0.6%  0.6% Water ad ad  100%  100% Sodium Chloride  0.5%  0.5% Urea 10.0% 10.0% Phenoxyethanol; Ethylhexylglycerin  0.7% (Euxyl PE 9010, Schülke & Mayr GmbH) Glyceryl Caprylate (dermosoft ® GMC; 0.35% Evonik Dr. Straetmans GmbH) Pentylene Glycol (dermosoft ® Pentiol  2.0% eco; Evonik Dr. Straetmans GmbH)

Recipes 27a and 27b: Quick-Breaking Cream

Recipe 27a 27b Composition from example 2  0.8%  0.8% Cetyl Dimethicone (ABIL ® Wax 9801,  1.6%  1.6% Evonik Operations GmbH) Diethylhexyl Carbonate (TEGOSOFT ®  4.0%  4.0% DEC, Evonik Operations GmbH) Dimethicone (ABIL ® 350, Evonik  1.0%  1.0% Operations GmbH) Cyclopentasiloxane  4.0%  4.0% Magnesium Stearate  0.3%  0.3% Water ad ad  100%  100% Propylene Glycol  5.0%  5.0% Sodium Chloride  1.0%  1.0% Methylisothiazolinone, Methylparaben,  0.8% Ethylparaben; Dipropylene Glycol (Microcare MEM, Thor) Glyceryl Caprylate (dermosoft ® GMC; 0.25% Evonik Dr. Straetmans GmbH) Phenylpropanol (dermosoft ® 250 eco; 0.35% Evonik Dr. Straetmans GmbH)

Recipes 28a, 28b and 28c: Cooling Body Lotion

Recipe 28a 28b 28c Composition from example 2  2.0%  1.5%  1.5% Polyglyceryl-4 —  0.5%  0.5% Diisostearate/Polyhydroxystearate/ Sebacate (ISOLAN ® GPS, Evonik Operations GmbH) Castor wax  0.5%  0.5%  0.5% Beeswax  0.5%  0.5%  0.5% Ethylhexyl Stearate (Tegosoft ® OS, 10.0% 10.0% 10.0% Evonik Operations GmbH) Diethylhexyl Carbonate (TEGOSOFT ®  8.5%  8.5%  8.5% DEC, Evonik Operations GmbH) Dimethicone (Belsil DM 5,  6.0%  6.0%  6.0% Wacker Chemical Corp.) Tocopheryl Acetate  0.5%  0.5%  0.5% Glycerin  3.0%  3.0%  3.0% Water ad ad ad  100%  100%  100% Sodium Chloride  1.0%  1.0%  1.0% Ethanol 20.0% 20.0% 20.0% Ethylhexylglycerin (dermosoft ®  0.5% EHG; Evonik Dr. Straetmans GmbH)

Recipes 29a, 29b and 29c: W/O Cream Based on Natural Ingredients

Recipe 29a 29b 23c Composition from example 2 3.0% 2.5% 2.5% Diisostearoyl Polyglyceryl-3 Dimer Dilinoleate — 0.5% 0.5% (ISOLAN ® PDI, Evonik Operations GmbH) Diethylhexyl Carbonate (TEGOSOFT ® DEC, 7.0% 7.0% 7.0% Evonik Operations GmbH) Oleyl Erucate (TEGOSOFT ® OER, Evonik 3.0% 3.0% 3.0% Operations GmbH) Almond oil 7.0% 7.0% 7.0% Shea butter 2.0% 2.0% 2.0% Cetyl Ricinoleate (TEGOSOFT ® CR, Evonik 1.0% 1.0% 1.0% Operations GmbH) Beeswax 0.6% 0.6% 0.6% Castor wax 0.4% 0.4% 0.4% Glycerin 5.0% 5.0% 5.0% Water ad ad ad  100%  100%  100% Magnesium sulfate heptahydrate 1.5% 1.5% 1.5% Sodium Benzoate, Potassium Sorbate (Euxyl K 0.5% 0.5% 712, Schülke & Mayr GmbH) Pentylene Glycol (dermosoft ® Pentiol eco; 3.0% Evonik Dr. Straetmans GmbH)

Recipes 30a, 30b and 30c: Cold-Preparable Lotion

Recipe 30a 30b 30c Composition from example 2  3.0%  2.5%  2.5% Polyglyceryl-3 Oleate (ISOLAN ® —  0.5%  0.5% GO 33, Evonik Operations GmbH) Isoamyl Coooate (TEGOSOFT ® AC,  5.0%  5.0%  5.0% Evonik Operations GmbH) Diethylhexyl Carbonate 12.0% 12.0% 12.0% (TEGOSOFT ® DEC, Evonik Operations GmbH) Phenoxyethyl Caprylate  4.0%  4.0%  4.0% (TEGOSOFT ® XC, Evonik Operations GmbH) Zinc Stearate  0.5%  0.5%  0.5% Water ad ad ad  100%  100%  100% Glycerin  3.0%  3.0%  3.0% Sodium Chloride  1.5%  1.5%  1.5% Phenoxyethanol; Ethylhexylglycerin  0.7%  0.7% (Euxyl PE 9010, Schülke & Mayr GmbH) Benzyl Alcohol; Caprylyl Glycol;  1.5% Benzoic Acid (Verstatil ® BOB; Evonik Dr. Straetmans GmbH)

Recipes 31a, 31b and 31c: Moisturizing Lotion Containing Urea

Recipe 31a 31b 31c Composition from example 2  2.0%  1.5%  1.5% Cetyl PEG/PPG-10/1 Dimethicone —  0.5%  0.5% (ABIL ® EM 180, Evonik Operations GmbH) Microcrystalline Wax  0.5%  0.5%  0.5% Castor wax  0.5%  0.5%  0.5% C12-15 Alkyl Benzoate  7.5%  7.5%  7.5% Oleyl Erucate (TEGOSOFT ® OER,  5.0%  5.0%  5.0% Evonik Operations GmbH) Ethylhexyl Palmitate (TEGOSOFT ®  5.0%  5.0%  5.0% OP, Evonik Operations GmbH) Caprylic/Capric Triglyceride  5.0%  5.0%  5.0% Glycerin  3.0%  3.0%  3.0% Urea 20.0% 20.0% 20.0% Magnesium sulfate heptahydrate  1.0%  1.0%  1.0% Water ad ad ad  100%  100%  100% Phenoxyethanol; Ethylhexylglycerin 0.70% 0.70% (Euxyl PE 9010, Schülke & Mayr GmbH) Parfum 0.10% 0.10% 0.10% Methylpropanediol; Phenoxyethanol;  1.5% Caprylyl Glycol (Verstatil ® MPC; Evonik Dr. Straetmans GmbH)

Recipes 32a, 32b, 32c and 32d: W/O Lotion with Light-as-Silk Skin Feel

Recipe 32a 32b 32c 33d Composition from example 2  2.5%  2.0%  2.0%  2.0% Cetyl PEG/PPG-10/1 Dimethicone (ABIL ® —  0.5% — — EM 90, Evonik Operations GmbH) Bis-PEG/PPG-14/14 Dimethicone; Dimethicone — —  1.0%  1.0% (ABIL ® EM 97 S, Evonik Operations GmbH) Microcrystalline Wax  0.1%  0.1%  0.1%  0.1% Castor wax  0.1%  0.1%  0.1%  0.1% Diethylhexyl Carbonate (TEGOSOFT ® DEC, 11.8% 11.8% 11.8% 11.8% Evonik Operations GmbH) Myristyl Myristate (TEGOSOFT ® MM, Evonik  1.0%  1.0%  1.0%  1.0% Operations GmbH) Dimethicone (Belsil DM 5, Wacker Chemical  8.0%  8.0%  8.0%  8.0% Corp.) Dimethicone (ABIL ® 350, Evonik Operations  0.5%  0.5%  0.5%  0.5% GmbH) Glycerin  3.0%  3.0%  3.0%  3.0% Magnesium sulfate heptahydrate  1.5%  1.5%  1.5%  1.5% Water ad ad ad ad  100%  100%  100  100% Benzyl Alcohol; Ethylhexylglycerin; Tocopherol  0.7%  0.7%  0.7% (Euxyl K 900, Schülke & Mayr GmbH) Phenoxyethanol; Ethylhexylglycerin (Verstatil ®  1.0% PE; Evonik Dr. Straetmans GmbH)

Recipes 33a, 33b and 33c: Baby-Care Product

Recipe 33a 33b 33c Composition from example 2  3.0%  2.0%  2.0% Paraffinum Liquidum; Petrolatum; —  1.0%  1.0% Ozokerite; Glyceryl Oleate; Lanolin Alcohol (PROTEGIN ® XN, Evonik Operations GmbH) Castor wax  0.1%  0.1%  0.1% Microcrystalline Wax  0.1%  0.1%  0.1% Oleyl Erucate (TEGOSOFT ® OER,  1.0%  1.0%  1.0% Evonik Operations GmbH) Isoamyl Cocoate (TEGOSOFT ® AC,  3.8%  3.8%  3.8% Evonik Operations GmbH) Ethylhexyl Palmitate (TEGOSOFT ®  1.0%  1.0%  1.0% OP, Evonik Operations GmbH) Almond oil  1.0%  1.0%  1.0% Zinc Oxide 20.0% 20.0% 20.0% Glycerin  3.0%  3.0%  3.0% Magnesium sulfate heptahydrate  1.0%  1.0%  1.0% Sodium Lactate; Sodium PCA; Glycine;  5.0%  5.0%  5.0% Fructose; Urea; Niacinamide; Inositol; Sodium Benzoate; Lactic Acid (LACTIL, Evonik Operations GmbH) Betaine (TEGO ® Natural Betaine,  3.0%  3.0%  3.0% Evonik Operations GmbH) Water ad ad ad  100%   100%   100%  Benzyl Alcohol; Ethylhexylglycerin;  0.7%  0.7% Tocopherol (Euxyl K 900, Schülke & Mayr GmbH) p-Anisio Acid (dermosoft ® 688; Evonik 0.12% Dr. Straetmans GmbH) Pentylene Glycol (dermosoft ® Pentiol  2.5% eco; Evonik Dr. Straetmans GmbH)

Recipes 34a, 34b and 34c: Foot-Care Product

Recipe 34a 34b 34c Composition from example 2 3.0% 2.5% 2.5% Petrolatum; Ozokerite; Hydrogenated — 0.5% 0.5% Castor Oil; Glyceryl Isostearate; Polyglycery-3 Oleate (PROTEGIN ® W, Evonik Operations GmbH) Castor wax 0.1% 0.1% 0.1% Microcrystalline Wax 0.1% 0.1% 0.1% Diethylhexyl Carbonate (TEGOSOFT ® 9.0% 9.0% 9.0% DEC, Evonik Operations GmbH) Ethylhexyl Palmitate (TEGOSOFT ® OP, 9.0% 9.0% 9.0% Evonik Operations GmbH) Stearyl Heptanoate (Tegosoft ® SH, 8.8% 8.8% 8.8% Evonik Operations GmbH) Glycerin 3.0% 3.0% 3.0% Magnesium sulfate heptahydrate 1.0% 1.0% 1.0% Ceramide NP; Ceramide AP; 5.0% 5.0% 5.0% Ceramide EOP; Phytosphingosine; Cholesterol; Sodium Lauroyl Lactylate; Carbomer; Xanthan Gum (SK-INFLUX V, Evonik Operations GmbH) Betaine (TEGO ® Natural Betaine, 3.0% 3.0% 3.0% Evonik Operations GmbH) Water ad ad ad 100%   100%   100%  Benzyl Alcohol; Ethylhexylglycerin; 0.7% 0.7% Tocopherol (Euxyl K 900, Schülke & Mayr GmbH) Phenoxyethanol; Benzoic Acid 1.0% (Verstatil ® BP; Evonik Dr. Straetmans GmbH)

Recipes 35a and 35b: Sunscreen Lotion SPF 30 UVA with Insect Repellent

Recipe 35a 35b Composition from example 2  3.0%  2.0% Polyglyceryl-2 —  1.0% Dipolyhydroxystearate (Dehymuls PGPH, BASF SE) Oleyl Erucate (TEGOSOFT ®  1.5%  1.5% OER, Evonik Operations GmbH) Diethylhexyl Carbonate  1.5%  1.5% (TEGOSOFT ® DEC, Evonik Operations GmbH) Diethylamino Hydroxybenzoyl  5.4%  5.4% Hexyl Benzoate (Uvinul A Plus, BASF SE) Ethylhexyl Methoxycinnamate 10.0% 10.0% Octocrylene  2.0%  2.0% Polyacrylamide; C13-14  2.1%  2.1% Isoparaffin; Laureth-7 (Sepigel 305, Seppic) Ethyl  4.0%  4.0% Butylacetylaminopropionate (R3535, Merck KGaA) Tocopheryl Acetate  0.5%  0.5% Glycerin  3.0%  3.0% Ethanol  0.5%  0.5% Magnesium sulfate  1.0%  1.0% heptahydrate Water ad ad  100%  100% Benzyl Alcohol;  0.7%  0.7% Ethylhexylglycerin; Tocopherol (Euxyl K 900, Schülke & Mayr GmbH) Parfum  0.1%  0.1%

Recipes 36a and 36b: Sunscreen Lotion SPF 30 UVA in Accordance with Ecocert Criteria

Recipe 36a 36b Composition from example 2  3.0%  2.0% Polyglycery/-3 Polyricinoleate (Cithrol PG3PR, —  1.0% (Croda Int. Plc) Isoamyl Cocoate (TEGOSOFT ® AC, Evonik  2.0%  2.0% Operations GmbH) Decyl Cocoate (TEGOSOFT ® DC, Evonik 10.0% 10.0% Operations GmbH) Isopropyl Palmitate (TEGOSOFT ® P, Evonik 10.0% 10.0% Operations GmbH) Zinc Oxide (Zinc Oxide PI, Symrise) 16.0% 16.0% Titanium Dioxide (nano); Alumina; Stearic Acid  9.0%  9.0% (Eusolex T-S, Merck KGaA) Water ad ad  100%  100% Glycerin  3.0%  3.0% Magnesium sulfate heptahydrate  1.0%  1.0% Sodium Benzoate, Potassium Sorbate (Euxyl K  0.5%  0.5% 712, Schülke & Mayr GmbH)

Recipes 37a, 37b, 37c and 37d: Sunscreen Spray SPF 30 UVA

Recipe 37a 37b 37c 37d Composition from example 2  3.0%  2.0%  3.6%  2.0% Cetyl PEG/PPG-10/1 Dimethicone (ABIL ® EM 90, —  1.0% — — Evonik Operations GmbH) Polyglyceryl-4 — — —  1.0% Diisostearate/Polyhydroxystearate/Sebacate (ISOLAN ® GPS, Evonik Operations GmbH) Diethylhexyl Carbonate (TEGOSOFT ® DEC, 13.0% 13.0% 11.3% 11.3% Evonik Operations GmbH) C12-15 Alkyl Benzoate 13.0% 13.0% 11.3% 11.3% Bis-Ethylhexyloxyphenol Methoxyphenyl  1.0%  1.0%  1.5%  1.5% Triazine (Tinosorb S, BASF SE) Butyl Methoxydibenzoylmethane — —  3.0%  3.0% Ethylhexyl Methoxycinnamate  5.0%  5.0% — — Octocrylene — —  6.0%  6.0% Homosalate — —  4.0%  4.0% Diethylamino Hydroxybenzoyl Hexyl Benzoate  5.0%  5.0% — — (Uvinul A Plus, BASF SE) Water ad ad ad ad  100%   100%   100%   100%  Glycerin  3.0%  3.0%  3.0%  3.0% Magnesium sulfate heptahydrate  1.0%  1.0%  1.0%  1.0% UV filter solution (20% Phenylbenzimidazole 15.0% 15.0% 15.0% 15.0% Sulfonic Acid (Eusolex 232, Merck KGaA, 8.8% tris(hydroxymethyl)aminomethane, water to 100%) Benzyl Alcohol; Ethylhexylglycerin; Tocopherol  0.7%  0.7%  0.7%  0.7% (Euxyl K 900, Schülke & Mayr GmbH)

Recipes 38a, 38b, 38c and 38d: Sunscreen Lotion SPF 50 UVA

Recipe 38a 38b 38c 38d Composition from example 2 3.0% 2.5% 3.0% 2.5% Cetyl PEG/PPG-10/1 Dimethicone (ABIL ® — 1.0% — 1.0% EM 90, Evonik Operations GmbH) Microcrystalline Wax 0.3% 0.3% 0.3% 0.3% Castor wax 0.3% 0.3% 0.3% 0.3% Diethylhexyl Carbonate (TEGOSOFT ® DEC, 2.4% 2.4% — — Evonik Operations GmbH) Phenoxyethyl Caprylate (TEGOSOFT ® XC, — — 3.9% 3.9% Evonik Operations GmbH) Bis-Ethythexyloxyphenol Methoxyphenyl Triazine 6.0% 6.0% — — (Tinosorb S, BASF SE) Diethylarino Hydroxybenzoyl Hexyl Benzoate 7.0% 7.0% 5.0% 5.0% (Uvinul A Plus, BASF SE) Butyl Methoxydibenzoylmethane — — 4.5% 4.5% Ethylhexyl Salicylate 3.0% 3.0% 5.0% 5.0% Ethylhexyl Methoxycinnamate 7.0% 7.0% — — Octocrylene — — 9.0% 9.0% Homosalate 3.0% 3.0% 5.0% 5.0% Ethylhexyl Triazone (Uvinul T 150, BASF SE) 1.0% 1.0% 2.0% 2.0% Titanium Dioxide; silica; Dimethicone (Parsol TX 2.0% 2.0% 2.0% 2.0% (DSM Nutritional Products Llc.) Water ad ad ad ad 100%  100%  100%  100%  Glycerin 3.0% 3.0% 3.0% 3.0% Magnesium sulfate heptahydrate 1.5% 1.5% 1.5% 1.5% Benzyl Alcohol; Ethylhexylglycerin; Tocopherol 0.7% 0.7% 0.7% (Euxyl K 900, Schülke & Mayr GmbH) Phenethylalcohol nat. 0.7%

Recipes 39a, 39b and 39c: Sunscreen Lotion SPF 50 in Accordance with FDA Criteria

Recipe 39a 39b 39c Composition from example 2  2.0%  1.5%  1.5% Lauryl PEG-10 Tris(Trimethylsiloxy) —  0.5%  0.5% Silylethyl Dimethicone (ES-5300 Formulation Aid, Dow Corning Corp.) Ethylhexyl Methoxycinnamate;  7.5%  7.5%  7.5% Diethylamino Hydroxybenzoyl Hexyl Benzoate (Uvinul A + B, BASF SE) Ethylhexyl Salicylate  5.0%  5.0%  5.0% Homosalate 15.0% 15.0% 15.0% Butyl Methoxydibenzoylmethane  3.0%  3.0%  3.0% Benzophenone-3  6.0%  6.0%  6.0% Octocrylene 10.0% 10.0% 10.0% Triisostearin  2.0%  2.0%  2.0% Microcrystalline Wax  1.2%  1.2%  1.2% Castor wax  0.8%  0.8%  0.8% Cetyl Dimethicone (ABIL ® Wax  2.0%  2.0%  2.0% 9801, Evonik Operations GmbH) Diethylhexyl Carbonate  2.0%  2.0%  2.0% (TEGOSOFT ® DEC, Evonik Operations GmbH) Water ad ad ad  100%  100%  100% Sodium Chloride  1.0%  1.0%  1.0% Ethylenediaminetetraacetic acid  0.1%  0.1%  0.1% Propylene glycol  3.0%  3.0%  3.0% Phenoxyethanol; Ethylhexylglycerin  0.7%  0.7% (Euxyl PE 9010, Schülke & Mayr GmbH) Verstatil PC  1.0%

Formulations 40a, 40b, 40c, 40d, 40e and 40f: Foundation

Recipe 40a 40b 40c 40d 40e 40f Composition from example 2  4.5%  2.5%  3.0%  2.5%  2.0%  2.0% Bis-(Glyceryl/Lauryl) —  2.0% — — — — Glyceryl Lauryl Dimethicone; Caprylic/Capric Triglyceride (ABIL ® EM 120, Evonik Operations GmbH) Polyglyceryl-4 Isostearate — —  1.0% — — — (ISOLAN ® GI 34, Evonik Operations GmbH) Cetyl Diglyceryl — — —  1.0% — — Tris(Trimethyisiloxy) Silylethyl Dimethicone (DC-5600, Dow Corning Corp.) Lauryl Polyglycery-3 — — — —  1.0% — Polydimethylsiloxyethyl Dimethicone (KF-6105, Shin-Etsu Chemical Co.) Polyglyceryl-4 Isostearate; — — — — —  2.0% Cetyl PEG/PPG-10/1 Dimethicone; Hexyl Laurate (ABIL^( ®) WE 09, Evonik Operations GmbH) Isoamyl Cocoate 10.8% 10.8% 10.8% 10.8% 10.8% 10.8% (TEGOSOFT ® AC, Evonik Operations GmbH) Oleyl Erucate (TEGOSOFT ®  8.0%  8.0%  8.0%  8.0%  8.0%  8.0% OER, Evonik Operations GmbH) Titanium Dioxide, Alumina,  4.0%  4.0%  4.0%  4.0%  4.0%  4.0% Triethoxy caprylyisilane (Hombitan AC360, Sachtleben) Iron Oxides (Sicovit Brown  2.1%  2.1%  2.1%  2.1%  2.1%   2.1% 70 E 172, Rockwood) Nylon-12 (TEGOLON ® 12-  2.0%  2.0%  2.0%  2.0%  2.0%  2.0% 20, Evonik Operations GmbH) Cyclopentasiloxane  3.5%  3.5%  3.5%  3.5%  3.5%  3.5% Disteardimonium Hectorite  1.0%  1.0%  1.0%  1.0%  1.0%  1.0% (Bentone 38 V CG, Elementis) Propylene carbonate  0.5%  0.5%  0.5%  0.5%  0.5%  0.5% Water ad ad ad ad ad ad  100%  100%  100%  100%  100%  100% Magnesium sulfate  1.5%  1.5%  1.5%  1.5%  1.5%  1.5% heptahydrate Glycerin  5.0%  5.0%  5.0%  5.0%  5.0%  5.0% Creatine (TEGO^( ®) Cosmo C  0.5%  0.5%  0.5%  0.5%  0.5%  0.5% 100, Evonik Operations GmbH) Ceteareth-25; Glycerin;  1.5%  1.5%  1.5%  1.5%  1.5%  1.5% Cetyl Alcohol; Behenic Acid; Cholesterol; Ceramide EOP; Ceramide EOS; Ceramide NP; Ceramide NS; Ceramide AP; Caprooyl Phytosphingosine; Caprooyl Sphingosine (SKINMIMICS, Evonik Operations GmbH) Benzyl Alcohol;  0.7%  0.7%  0.7%  0.7%  0.7%  0.7% Ethylhexylglycerin; Tocopherol (Euxyl K 900, Schulke & Mayr GmbH)

Formulations 41a, 41b, 41c, 41d, 41e, 41f and 41g: CC (Colour Control) Fluid

Recipe 41a 41b 41c 41d 41e 41f 41g Composition from example 2  3.0%  2.0%  2.5%  3.0%  2.5%  2.0%  1.0% Polyglyceryl-4 —  1.0% — — — — — Diisostearate/Polyhydroxyste arate/Sebacate (ISOLAN ® GPS, Evonik Operations GmbH) Sorbitan Oleate (TEGO ® — —  0.5% — — — — SMO V, Evonik Operations GmbH) PEG-30 — — —  1.0% — — — Dipolyhydroxystearate (Arlacel P135, Croda) Polyglycery-3 Diisostearate — — — —  1.5% — — (Lameform TGI, BASF SE) Glyceryl Oleate, Polyglyceryl- — — — — —  1.0% — 3 Polyricinoleate, Olea Europaea (olive) Oil Unsaponifiables (Plantasens Natural Emulsifier CP5, Clariant) Lauryl PEG-9 — — — — — —  1.0% Polydimethylsiloxyethyl Dimethicone (KF-6038, Shin- Etsu Chemical Co.) Ethylhexyl 10.0% 10.0% 10.0% 10.0% 10.0% 10.0% 10.0% Methoxycinnamate; Diethylamino Hydroxybenzoyl Hexyl Benzoate (Uvinul A + B, BASF SE) Cyclopentasiloxane  3.5%  3.5%  3.5%  3.5%  3.5%  3.5%  3.5% Disteardimonium Hectorite  1.0%  1.0%  1.0%  1.0%  1.0%  1.0%  1.0% (Bentone 38 V CG, Elementis) Propylene carbonate  0.5%  0.5%  0.5%  0.5%  0.5%  0.5%  0.5% Titanium Dioxide, Alumina,  4.0%  4.0%  4.0%  4.0%  4.0%  4.0%  4.0% Triethoxycaprylyisilane (Hombitan AC360, Sachtleben) Talc  2.0%  2.0%  2.0%  2.0%  2.0%  2.0%  2.0% Iron Oxides;  0.4%  0.4%  0.4%  0.4%  0.4%  0.4%  0.4% Triethoxycaprylyisilane (Unipure Yellow LC 182 AS- EM, Sensient) iron Oxides; 0.12% 0.12% 0.12% 0.12% 0.12% 0.12% 0.12% Triethoxycaprylyisilane (Unipure Red LC 381 AS- EM, Sensient) iron Oxides; 0.08% 0.08% 0.08% 0.08% 0.08% 0.08% 0.08% Triethoxycaprylyisilane (Unipure Black LC 989 AS- EM, Sensient) Diethylhexyl Carbonate  4.0%  4.0%  4.0%  4.0%  4.0%  4.0%  4.0% (TEGOSOFT ® DEC, Evonik Operations GmbH) C12-15 Alkyl Benzoate  4.0%  4.0%  4.0%  4.0%  4.0%  4.0%  4.0% isopropyl Palmitate  4.0%  4.0%  4.0%  4.0%  4.0%  4.0%  4.0% (TEGOSOFT ® P, Evonik Operations GmbH) Nylon-12 (TEGOLON ® 12-  2.0%  2.0%  2.0%  2.0%  2.0%  2.0%  2.0% 20, Evonik Operations GmbH) Water ad ad ad ad ad ad ad  100%  100%  100%  100%  100%  100%  100% Glycerin  5.0%  5.0%  5.0%  5.0%  5.0%  5.0%  5.0% Sodium Chloride  1.5%  1.5%  1.5%  1.5%  1.5%  1.5%  1.5% Tetrapeptide-30; Glycerin  0.3%  0.3%  0.3%  0.3%  0.3%  0.3%  0.3% (TEGO ® Pep 4-Even, Evonik Operations GmbH) Phenoxyethanol;  0.7%  0.7%  0.7%  0.7%  0.7%  0.7%  0.7% Methylparaben; Ethylparaben; Propylparaben (Phenonip XB, Clariant)

Recipes 42a, 42b, 42c, 42d and 42e: Antiperspirant/Deodorant Spray or Aerosol Spray

Recipe 42a 42b 42c 42d 42e Composition from  3.0%  2.0%  3.0%  2.0%  2.0% example 2 Polyglyceryl-4 —  1.0% —  1.0%  1.0% Diisostearate/ Polyhydroxy- stearate/Sebacate (ISOLAN ® GPS, Evonik Operations GmbH) Isopropyl Palmitate 20.0% 20.0% 20.0% 20.0% 20.0% (TEGOSOFT ® P, Evonik Operations GmbH) Diethylhexyl Carbonate  7.0%  7.0%  7.0%  7.0%  7.0% (TEGOSOFT ® DEC, Evonik Operations GmbH) Triethyl Citrate  5.0% (dermofeel ® TEC eco; Evonik Dr. Straetmans GmbH) Water ad ad ad ad ad  100%  100%  100%  100%  100% Glycerin  2.0%  2.0%  2.0%  2.0%  2.0% Aluminium Chlorohydrate 30.0% 30.0% 30.0% 30.0% 30.0% (50% aq.; Locron LIC, Clariant AG) Parfum  1.0%  1.0%  1.0%  1.0%  1.0% Propellant — — Mix emulsions 42c and 42d with propellant in mass ratio of 5:2 Phenoxyethanol; Caprylyl  0.8% Glycol (Vestatil ® PC; Evonik Dr. Straetmans GmbH)

Recipes 43a, 43b, 43c and 43d: Sunscreen Aerosol SPF 50 UVA

Recipe 43a 43b 43c 43d Composition from example 2  4.0%  4.0%  4.0%  4.0% Cetyl PEG/PPG-10/1 Dimethicone — —  1.0%  1.0% (ABIL ® EM 90, Evonik Operations GmbH) C12-15 Alkyl Benzoate 10.0%  8.0% 10.0%  8.0% Diethylhexyl Carbonate 13.0% 10.0% 13.0% 10.0% (TEGOSOFT ® DEC, Evonik Operations GmbH) Bis-Ethylhexyloxyphenol  4.0%  4.0%  4.0%  4.0% Methoxyphenyl Triazine (Tinosorb S, BASF SE) Diethylamino Hydroxybenzoyl Hexyl  5.0%  5.0%  5.0%  5.0% Benzoate (Uvinul A Plus, BASF SE) Ethylhexyl Salicylate  5.0%  5.0%  5.0%  5.0% Ethylhexyl Methoxycinnamate  4.0%  4.0%  4.0%  4.0% Water ad ad ad ad  100%  100%  100%  100% Glycerin  3.0%  3.0%  3.0%  3.0% UV filter solution (20% 20.0% 20.0% 20.0% 20.0% Phenylbenzimidazole Sulfonic Acid (Eusolex 232, Merck KGaA, 8.8% tris(hydroxymethyl)aminomethane, water to 100%) Magnesium sulfate heptahydrate  1.0%  1.0%  1.0%  1.0% Benzyl Alcohol; Ethylhexylglycerin;  0.7%  0.7%  0.7%  0.7% Tocopherol (Euxyl K 900, Schülke & Mayr GmbH) Mix emulsions 43a, 43b, 43c and 43d with propellant in mass ratio of 2:1

Formulation 44: Shower Cream

Water ad  100.0% Composition from example 1  1.5% Sodium Laureth Sulfate (Texapon NSO, BASF, 28%)  25.0% Coco-Glucoside (Plantacare 818 UP, BASF, 51%)  8.0% Cocamidopropy Betaine (TEGO ® Betain F 50, Evonik, 38%)  8.0% PEG-18 Glyceryl Oleate/Cocoate (ANTIL ® 171, Evonik)  1.5% Sorbitan Sesquicaprylate (ANTIL ® Soft SC, Evonik)  0.8% Glyceryl Oleate (TEGIN ® O V, Evonik)  0.8% Perfume Spicy Herbs (IFF)  0.2% Polyglyceryl-4 Caprate (TEGOSOFT ® PC 41, Evonik)  0.6% Helianthus Annuus Seed Oil (AEC Sunflower Oil, A & E  0.2% Connock, Perfumery & Cosmetics Ltd.)   Linalool (Lipofresh, Lipo Chemicals, Inc.)  0.1% Coumarin (Rhodiascent extra pure, Solvay Rhodia)  0.1% Glycerin (Glycerol EP, vegetable, Spiga Nord)  0.4% Hydroxypropyl Methylcellulose (TEGOCEL ® HPM 50, Evonik)  0.2% Glycol Distearate (TEGIN ® G 1100 Pellets, Evonik)  0.4% Sodium Chloride  0.5% Hydroxypropyl Guar Hydroxypropyltrimonium  0.2% Chloride (Jaguar C-162, Solvay Rhodia)   dermofeel TOCO 70 non GMO  0.1% Disodium EDTA (Dissolvine NA-2-P, AkzoNobel)  0.1% Preservative q.s. Citric Acid ad pH 5.2

Formulation 45: Body Shampoo

Phase A Composition from example 1  5.0% Lavandula Angustifolia (lavender) Oil  0.2% (AEC Lavender Oil, A & E Connock Ltd.)   Perfume  0.1% Phase B Sodium Cocoamphoacetate  10.0% (REWOTERIC ® AM C, Evonik, 32%) Phase C Water ad 100.0% Xanthan Gum (Keitrol CG-SFT, CP Kelco)  1.2% Phase D Sodium Lauroyl Methyl Isethionate (Iselux,  4.5% innospec Active Chemicals)   Capryl/Capramidopropyl Betaine  4.5% (TEGO ® Betaine 810, Evonik, 38%)   Citric Acid  1.2% Phase E Water  10.0% Polyquaternium-7 (Merquat 550, Nalco)  0.4% Preservative q.s

Formulation 46: Shampoo

Phase A Composition from example 1  3.5% Isopropyl Myristate (TEGOSOFT ® M,  0.2% Evonik) Perfume  0.1% Phase B Water ad 100.0% Phase C Sodium Lauryl Suifate (Texapon LS 35,  28.0% BASF, 30%) Phase D Cocamidopropyl Betaine (TEGO ® Betain F  9.0% 50, Evonik, 38%) Phase E Cocamide MEA (REWOMID ® C 212, Evonik)  2.0% Xanthan Gum (Keitrol CG-SFT, CP Kelco)  0.3% Water  10.0% Phase F Water  10.0% Polyquaternium-10 (Polymer JR 400,  0.2% Amerchol) Phase G Citric Acid ad pH 5.0 Phase H Preservative q.s.

Recipes 47a and 47b: Shampoo

Recipes 47a 47b Water ad ad 100.0% 100.0% Composition from example 1  2.5%  2.5% Composition from example 3  1.5%  1.5% Cocamidopropyl Betaine (TEGO ® Betain F 50, Evonik, 38%)  22.0%  22.0% Lauryl Glucoside (Plantacare 1200 UP, BASF, 50%)  6.0%  6.0% Sodium Cocoyl Glutamate (Plantapon ACG HC, BASF)  1.5%  1.5% Sodium Cocoyl Glycinate (Hostapon SG, Clariant)  0.8%  0.8% Zinc Pyrithione (Microcare ZP, Thor)  0.1%  0.1% PEG-120 Methyl Glucose Dioleate (ANTIL ® 120 Plus, Evonik)  0.4%  0.4% Sodium Chloride  0.5%  0.5% Isostearamide MIPA; Glyceryl Laurate (ANTIL ® SPA 80, Evonik)  0.5%  0.5% Xanthan Gum (Keltrol CG-SFT, CP Kelco)  0.3%  0.3% Hydroxypropyl Guar Hydroxypropyltrimonium Chloride (Jaguar  0.3%  0.3% C-162, Solvay Rhodia)   Quaternium-80 (ABIL ® Quat 3272, Evonik)  0.4%  0.4% Palmitamidopropyltrimonium Chloride (VARISOFT ® PATC,  0.4%  0.4% Evonik)     Argania spinosa oil (Argan Oil, DSM Nutritional Products Ltd.)  0.1%  0.1% Glycerin (Glycerol EP, vegetable, Spiga Nord)  0.6%  0.6% Tetrasodium EDTA (Versene 100, The Dow Chemical  0.1%  0.1% Company) Caffeine (Merck KGaA/EMD Chemicals, Inc.)  0.1%  0.1% Hydrolyzed Wheat Protein (Gluadin WLM, BASF)  0.1%  0.1% Limonene (Dipentene No. 122, Hercules Inc.)  0.1%  0.1% Citric Acid ad pH 5.5 ad pH 5.5 Sodium Phytate; Aqua; Alcohol (dermofeel ® PA-3; Evonik Dr.  0.1% Straetmans GmbH (PA-3) Perfume  0.2% Preservative q.s. Aqua; Sodium Levulinate; Sodium Benzoate (Verstatil ® BL non-  1.2% GMO; Evonik Dr. Straetmans GmbH)

Formulation 48: Liquid Soap

Water ad  100% Glycerin (Glycerol EP, vegetable, Spiga Nord)  4.0% Alcohol  4.0% Sodium Coco-Sulfate (Texapon HC G, BASF)  3.0% Lauryl Glucoside (Plantacare 1200 UP, BASF, 50%)  6.0% Composition from example 1  3.0% Xanthan Gum (Keltrol CG-SFT, CP Kelco)  1.5% Mangifera Indica (mango) Fruit Extract (Mango Extract, Draco  0.5% Natural Products)   Limonene (Dipentene No. 122, Hercules Inc.)  0.1% Linalool (Lipofresh, Lipo Chemicals, Inc.)  0.1% Citric Acid ad pH 4.9 Preservative q.s. Dyes q.s.

Formulation 49: Cream Soap

Wafer ad  100% Propylene Glycol (Euxyl K 320, Schülke & Mayr GmbH)  2.0% Coco-Glucoside (Plantacare 818 UP, BASF, 51%) 10.0% Glycerin (Glycerol EP, vegetable, Spiga Nord)  5.0% Composition from example 1  2.5% Disodium Cocoyl Glutamate (Planatpon ACG LC, BASF)  2.5% Xanthan Gum (Keltrol CG-SFT, CP Kelco)  1.2% Stearic Acid (Pristerene 4922, Croda Europe, Ltd.)  1.2% Citric Acid ad pH 5.5 Olea Europaea Fruit Oil (Cropure Olive, Croda Europe, Ltd.)  0.2% Glyceryl Oleate (TEGIN ® O V, Evonik)  1.0% Sodium Cocoyl Glutamate (Plantapon ACG HC, BASF)  0.8% Tetrasodium EDTA (Versene 100, The Dow Chemical  0.2% Company)   Perfume  0.1% Preservative q.s. Dyes q.s.

Formulation 50: Oil Bath

Water to 100.0% Glycine Soja Oil (Cropure Soybean, Croda Europe, Ltd.)  20.0% Composition from example 1  12.0% Polyglyceryl-3 Palmitate (Dermofeel ® PP, Evonik Dr.  4.5% Straetmans) Glyceryl Caprylate (Dermosoft ® GMCY, Evonik Dr. Straetmans)   3.0% Simmondsia Chinensis Seed Oil (AEC Jojoba Oil Refined, A & E   1.2% Connock, Perfumery & Cosmetics Ltd.)    Primus Amygdalus Duicis (sweet almond) Oil (Cropure Almond,   1.0% Croda Europe, Ltd.)    Triticum Vulgare Germ Oil (Cropure Wheatgerm, Croda Europe,   0.5% Ltd.)    Tocopherol (Euxyl K 700, Schülke & Mayr GmbH)   0.2% Limonene (Dipentene No. 122, Hercules Inc.)   0.1% Citral   0.1% Preservative q.s. Dyes q.s.

Formulation 51: Micellar Water for Makeup Removal

Water ad 100.0% Perfume  0.1% Composition from example 1  2.0% Capryl/Capramidopropyl Betaine (TEGO ® Betain 810, Evonik,  1.3% 38%)   Polyglyceryl-6 Caprylate; Polyglyceryl-3 Cocoate; Polyglyceryl-4  1.0% Caprate; Polyglyceryl-6 Ricinoleate (TEGO ® Solve 61, Evonik)   Betaine (TEGO ® Natural Betaine, Evonik)  2.0% Glycerin (Glycerol EP, vegetable, Spiga Nord)  1.0% Preservative q.s

Recipes 52a and 52b: Solution for Wet Wipes

Recipe 52a 52b Composition from example 1  3.5%  3.5% Aloe Barbadensis Leaf Extract (Aloe-Con UP 40, Florida Food  0.2%  0.2% Products Inc.)     Isopropyl Myristate (TEGOSOFT ® M, Evonik)  0.2%  0.2% Disodium Cocoamphodiacetate (REWOTERIC ® AM 2 C NM,  1.5%  1.5% Evonik, 39%)     Perfume  0.2%  0.2% Propylene Glycol (Euxyl K 320, Schülke & Mayr GmbH)  2.5%  2.5% Hydrolyzed Silk (Crosilk 10000, Croda Inc.)  0.2%  0.2% Caprylyl/Capryl Glucoside (Plantacare 810 UP, BASF)  1.0%  1.0% Water ad ad 100.0% 100.0% Citric Acid ad pH 5.0 ad pH 5.0 Phenoxyethanol (S&M Phenoxyethanol, Schülke & Mayr GmbH)  0.5%  0.5% Dehydroacetic Acid (Unisept DHA (Universal Preserv-A-Chem,  0.1%  0.1% Inc.)     Sodium Benzoate (Euxyl K 712, Schülke & Mayr GmbH)  0.4%  0.4% Salicylic Acid (salicylic acid nat.; Evonik Dr. Straetmans GmbH)    0.5%

Formulation 53: Antiperspirant Deodorant

Phase A Composition from example 1   4.0% Dicaprylyl Ether (Cetiol OE, BASF)   0.3% Geraniol (Nerol 800, International Flavors &   0.1% Fragrances Inc.)    Linalool (Lipofresh, Lipo Chemicals, Inc.)   0.1% Perfume   0.1% Phase B Propylene Glycol (Euxyl K 320, Schülke & Mayr   1.0% GmbH)    Butylene Glycol (Oxea Corparation)   0.2% Water   5.0% Palmitamidopropyltrimonium Chloride   1.0% (VARISOFT ® PATC, Evonik)   Phase C Water  50.0% Hydroxethyl ethylcellulose (Structure Cel 4400 E,   0.8% AkzoNobel)    Sodium Hydroxide (10% in water)   0.3% Phase D Aluminium Chiorohydrate (Locron L, Cladant)  15.0% Phase E Preservative q.s. Water ad 100.0%

Formulation 54: Mouthwash

Composition from example 1  0.4% Glycolipids (Rheance One, Evonik)  0.2% Flavour  0.2% Water ad 100.0% Sorbitol (Karion FP Liquid, Merck)  3.0% Preservative q.s. Dyes q.s.

Formulation 55: Toothpaste

A Sorbitol (Karion FP Liquid, Merck)  50.0% Water ad 100.0% Sodium carboxymethyl cellulose (Blanose  1.2% 7MXF, Ashland)   B Sodium Saccharin (Sigma Aldrich)  0.1% Sodium Fluoride (Sigma Aldrich)  0.1% C Titanium Dioxide (Caesar & Loretz)  0.4% Hydrated Silica (Zeodent ® 113, Evonik)  14.0% Hydrated Silica (Zeodent ® 165, Evonik)  8.0% D Flavour oil  1.0% E Glyceryl Caprylate (dermosoft ® GMCY, Evonik)  0.3% Composition from example 1  3.5% 

1. A process for enzymatic preparation of a sorbitol carboxylate, comprising: A) blending sorbitol and at least one acyl group donor, within a temperature range of 80° C. to 120° C., for at least 10 minutes. B) reacting the sorbitol with the at least one acyl group donor in the presence of a lipase at a temperature of 75° C. to 110° C., to give a sorbitol carboxylate, and C) optionally, purifying the sorbitol carboxylate.
 2. The process according to claim 1, wherein the at least one acyl group donor provided in A) provides acyl groups that derive from a carboxylic acid containing 2 to 34 carbon atoms or a mixture thereof.
 3. The process according to claim 1, wherein the sorbitol and the at least one acyl group donor make up at least 80% by weight, based on an overall reaction mixture at the start of B).
 4. The process according to claim 1, wherein in B), a water content based on an overall reaction mixture is less than 15% by weight.
 5. The process according to claim 1, wherein the lipase is selected from the group consisting of a lipase from Thermomyces lanuginosus, a lipase A or B from Candida antarctica, a lipase from Mucor miehei, a lipase from Humicola sp., a lipase from Rhizomucor javanicus, a lipase from Rhizopus oryzae, a lipase from Candida rugosa, a lipase from Rhizopus niveus, a lipase from Penicillium camemberti, a lipase from Aspergillus niger, a lipase from Penicillium cyclopium, and a respective at least 60% homologue thereof at an amino acid level.
 6. The process according to claim 1, wherein B) is conducted at a pressure of less than 1 bar.
 7. The process according to claim 1, wherein B) is ended no later than 180 hours after the lipase has been added.
 8. The process according to claim 1, wherein a molar ratio of the sorbitol provided to all acyl groups present in the at least one acyl group donor provided is within a range from 1.00:0.50 to 1.00:5.00.
 9. A sorbitol carboxylate obtainable by the process according to claim
 1. 10. The sorbitol carboxylate according to claim 9, containing: at least one carboxylic ester of sorbitol, and at least one of a carboxylic ester of 1,4-anhydrosorbitol, a carboxylic ester of 2,5-anhydrosorbitol, a carboxylic ester of 1,5-anhydrosorbitol, and a carboxylic ester of isosorbide, where a ratio by weight of sorbitol residues present in the sorbitol carboxylate to a sum total of all 1,4-anhydrosorbitol residues, 2,5-anhydrosorbitol residues, 1,5-anhydrosorbitol residues, and isosorbide residues present in the sorbitol carboxylate is greater than 90:10, wherein a molar ratio of esterified primary hydroxyl groups to esterified secondary hydroxyl groups in the at least one carboxylic ester of sorbitol is 80:20 to 20:80.
 11. The sorbitol carboxylate according to claim 9, wherein an average degree of esterification of the at least one carboxylic ester of sorbitol present is from 0.3 to 4.0.
 12. The sorbitol carboxylate according to claim 9, wherein the sorbitol carboxylate contains 0.05% to 40% by weigh of free sorbitol.
 13. The sorbitol carboxylate according to claim 9, wherein the sorbitol carboxylate contains less than 25% by weight of at least one free carboxylic acid.
 14. The sorbitol carboxylate according to claim 9, wherein a total monoester content of the at least one carboxylic ester of sorbitol contains from 5% by weight to 25% by weight of secondary ester regioisomers.
 15. The sorbitol carboxylate according to claim 9, wherein the sorbitol carboxylate is a viscosity regulator, a care active ingredient, a foam booster or solubilizer, an antimicrobial, an antistat, a binder, a corrosion inhibitor, a dispersant, an emulsifier, a film former, a humectant, an opacifier, an oral care agent, a preservative, a skincare agent, a hydrophilic emollient, a foam stabilizer, or a nonionic surfactant.
 16. The process according to claim 1, wherein the at least one acyl group donor is selected from the group consisting of a fatty acid ester and a fatty acid.
 17. The process according to claim 1, wherein in B), the reacting is at a temperature of 80° C. to 95° C.
 18. The process according to claim 1, wherein in A), the blending is at a temperature range of 100° C. to 120° C., for at least 60 minutes.
 19. The process according to claim 2, wherein the at least one acyl group donor is a natural fatty acid or a mixture thereof.
 20. The process according to claim 3, wherein the sorbitol and the at least one acyl group donor make up at least 95% by weight, based on the overall reaction mixture at the start of B). 